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Atomic and Nano Scale Materials for Advanced Energy Conversion
Atomic and Nano Scale Materials
for Advanced Energy Conversion
Volume 1
Edited by Zongyou Yin

Editor All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Zongyou Yin publisher do not warrant the information
Australian National University contained in these books, including this book,
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v
Contents
Volume 1
1 Introduction 1
Zongyou Yin
Part I Emerging Nanomaterials for Electrochemical (EC)

Energy Conversion 3
2 2D-Materials-Free Heterostructures for EC Energy

Conversion 5
Kamran Dastafkan and Chuan Zhao
2.1 Heterostructures for Electrochemical Water Splitting 5
2.1.1 Metal Oxide-Based Heterostructures 5
2.1.2 Metal Hydroxide-Based Heterostructures 9
2.1.3 Metal Pnictide-Based Heterostructures 10
2.1.4 Metal Chalcogenide-Based Heterostructures 11
2.1.5 Metal/Carbon-Based Heterostructures 15
2.1.6 Mixed-Phase Metallic Heterostructures 16
2.1.7 Multicomponent Metal-Based Heterostructures 17
2.1.7.1 Metal Oxide-Based Multicomponent Heterostructures 17
2.1.7.2 Metal Non-oxide-Based Multicomponent Heterostructures 22
2.1.7.3 Mixed Metal Oxide/Metallic Non-oxide Multicomponent
Heterostructures 24
2.2 Heterostructures for Electrochemical CO2 Reduction Reaction 24
2.2.1 Metal/Metal Oxide-Based Heterostructures 25
2.2.3 Metal/Heteroatom-Doped Porous Carbon-Based Heterostructures 29
2.2.4 Metal Oxide/Porous Carbon-Based Heterostructures 31
2.2.5 Metal Non-oxide-Based Heterostructures 31
2.2.6 Multicomponent Metal-Based Heterostructures 32
2.2.6.1 Metal Oxide-Based Multicomponent Heterostructures 34
2.3 Heterostructures for Electrochemical N2 Reduction Reaction 38
vi Contents
2.3.2 Metal/Heteroatom-Doped Porous Carbon-Based Heterostructures 39

2.3.3 Metal Non-oxide-Based Heterostructures 41
2.4 Challenges and Future Opportunities 43
References 45
3 2D-Materials-Based Heterostructures for EC Energy

Conversion 53
Zhengqing Liu
3.1 Advances of 2D Materials-Based Heterostructures 53
3.2 Water Splitting 54
3.2.1 Hydrogen Evolution Reaction (HER) 68
3.2.1.1 HER on 2D–0D Heterostructures 68
3.2.1.3 HER on 2D–2D (van der Waals) Heterostructures 73
3.2.2 Oxygen Evolution Reaction (OER) 80
3.2.2.1 OER on 2D–0D Heterostructures 80
3.2.2.3 OER on 2D–2D (van der Waals) Heterostructures 85
3.2.3 Overall Water Splitting (OWS) 90
3.2.3.1 OWS on 2D Binary/Ternary Compounds 91
3.2.3.2 OWS on Heteroatom-Doped 2D Materials 93
3.2.3.3 OWS on 2D–0D Heterostructures 95
3.2.3.5 OWS on 2D–2D (van der Waals) Heterostructures 98
3.3 CO2 Reduction Reaction (CRR) 103
3.3.1 CRR on 2D–0D Heterostructures 105
3.3.2 CRR on 2D–1D Heterostructures 106
3.3.3 CRR on 2D–2D (van der Waals) Heterostructures 107
3.4 N2 Reduction Reaction (NRR) 109
3.4.1 NRR on 2D–0D Heterostructures 110
3.5 Challenge and Opportunity 117
References 118
4 Superlattices for EC Energy Conversion 129

Hang Yin and Zongyou Yin
4.1 EC Water Splitting 129
4.1.1 EC Hydrogen Evolution Reaction (HER) 129
4.1.2 EC Oxygen Evolution Reaction (OER) 132
4.1.3 EC Overall Water Splitting (OWS) 137
4.2 EC CO2 Reduction Reaction (CRR) 143
References 145
Contents vii
5 Polymorphic Phase Engineered Structures (PPESs) for EC

Energy Conversion 147
Nasir Uddin, Ziyang Lu, and Zongyou Yin
5.1 Introduction 147
5.2 PPES for EC Water Splitting 148
5.2.1 EC Hydrogen Evolution Reaction (HER) 150
5.2.1.1 EC-HER on Single Phases 151
5.2.1.2 EC-HER on Hetero-phases 152
5.2.1.3 EC-HER on Multi-phases 155
5.2.2 EC Overall Water Splitting (OWS) 156
5.2.2.1 EC OWS on Single Phases 157
5.2.2.2 EC OWS on Hetero-Phases 158
5.3 PPES for EC N2 Reduction Reaction (NRR) 160
5.3.1 EC NRR on Crystalline Phases 160
5.3.2 EC NRR on Amorphous Phases 164
References 167
6 Rare-earth Nanomaterials for EC Energy Conversion 171

Tong Wu, Mingzi Sun, Bolong Huang, and Yaping Du
6.1 Rare Earth Nanomaterials for EC Reactions 171
6.1.1 Simple Oxides 171
6.1.1.1 EC N2 Reduction Reaction (NRR) on Y2 O3 Nanosheet 171
6.1.2 Alloys and Intermetallics 174
6.1.2.1 EC Hydrogen Evolution Reaction (HER) 174
6.1.3 Ce-doping and CeO2 -incorporated Transition Metal-based
Catalysts 180
6.1.3.1 EC Hydrogen Evolution Reaction (HER) 180
6.1.3.2 EC Oxygen Evolution Reaction (OER) 183
6.1.3.3 EC N2 Reduction Reaction on Bi4 V2 O11 /CeO2 185
References 188
Part II Emerging Nanomaterials for Photochemical (PC)

7 2D-Materials Free Heterostructures for photochemical Energy

Conversion 193
Wei Chen and Guohua Jia
7.1 2D-Materials Free Heterostructures 193
7.1.1 Heterostructure for PC Water Splitting 198
7.1.1.1 Metal Chalcogenide/Phosphide Semiconductor–Semiconductor
Heterostructure 198
7.1.1.2 Oxide (TiO2 ) Semiconductor–Semiconductor Heterostructure 200
7.1.1.3 Non-noble Metals and Semiconductor Heterostructures 204
7.1.1.4 Other Heterostructures 204
viii Contents
7.1.2 PC CO2 Reduction Reaction 207

7.1.2.1 TiO2 Based Semiconductor Heterostructures 212
7.1.2.2 Chalcogenide/Oxide Semiconductor-Based Heterostructures 212
7.1.2.3 Other Heterostructures 218
7.1.3 PC N2 Reduction Reaction 218
7.1.4 Challenge and Opportunity 221
References 222
8 Van der Waals Heterostructures in Photocatalytic Energy

Conversion 225
Bikesh Gupta, Han Li, Julie Tournet, Hark H. Tan, Chennupati Jagadish,
Shaowen Cao, and Siva K. Karuturi
8.2 Fabrication of 2D/2D Heterostructures 226
8.2.1 Vertical Heterostructures 226
8.2.1.1 Mechanical Exfoliation and Transfer 226
8.2.1.2 Chemical Vapor Deposition 228
8.2.1.3 Liquid-Based Techniques 229
8.2.1.4 Liquid-Phase Assembly 229
8.2.1.5 Layer-by-Layer Assembly 231
8.2.2 Lateral Heterostructures 234
8.3 2D/2D Heterostructures for Photocatalytic Redox Reactions 236
8.3.1 Water Splitting 239
8.3.2 CO2 Reduction 243
8.3.3 N2 Reduction 246
8.3.4 Fuel Cells 248
8.4 Mixed-Dimensional Heterostructures for Photocatalytic Redox
Reaction 249
8.4.2 CO2 Reduction 253
8.4.3 N2 Reduction 257
8.4.4 Fuel Cells 260
8.5 Challenges and Perspectives 260
8.5.1 Precise Control over the Optical, Electronic, and Structural
Properties 261
8.5.2 Mechanistic Understanding of Catalysis 261
8.5.3 Commercial Applications 261
Acknowledgments 262
References 262
9 Superlattices for PC Energy Conversion 275

Hang Yin and Zongyou Yin
9.1 PC Water Splitting 275
9.1.1 PC Hydrogen Evolution Reaction (HER) 275
9.1.2 PC Overall Water Splitting (OWS) 279
References 282
Contents ix
10 Polymorphic Phase Engineered Structures (PPESs) for PC

Nasir Uddin, Ziyang Lu, and Zongyou Yin
10.1 PPES for PC Water Splitting 285
10.1.1.1 PC-HER on Single Phases 286
10.1.1.2 PC-HER on Heterophases 288
10.1.1.3 PC-HER on Multiphases 289
10.1.2.1 PC OWS on Heterophases 291
10.1.2.2 PC OWS on Multiphases 292
10.2 PPES for PC CO2 Reduction Reaction (CRR) 294
10.2.1 PC CRR on Single Phases 295
10.2.2 PC CRR on Multiphases 297
10.3 PPES for PC N2 Reduction Reaction (NRR) 300
10.3.1 PC-NRR on Single Phases 300
10.3.2 PC-NRR on Heterophases 302
References 304
11 Rare-earth Nanomaterials for PC Energy Conversion 309

11.1 Complex Oxides 309
11.1.1 Perovskites 309
11.1.1.1 PC-HER 309
11.1.1.2 PC CO2 Reduction Reaction 311
11.1.2 Tantalates 311
11.1.2.1 PC-HER on K4 Ce2 Ta10 O∼30 311
11.1.3 Niobates 314
11.1.3.1 PC-HER on H1−x Lax Ca2−x Nb3 O10 314
11.2 Ce-Based Photocatalysts 317
11.2.1 PC-HER on CdS/CeO2 317
11.2.2 PC-NRR on CeO2 /FeS2 319
References 321
12 Non-noble Plasmonic Enhancement (NNPE) for PC Energy

Conversion 325
Chao Yang and Shaowen Cao
12.2 NNPE Water Splitting 326
12.2.1.1 PC HER on Non-noble Metals 326
12.2.1.2 PC HER on Non-noble Metal Oxides 327
12.2.1.3 PC HER on Other Non-noble Metal Compounds 328
12.2.2 PC Oxygen Evolution Reaction (OER) 328
x Contents
12.3 NNPE CO2 Reduction Reaction (CRR) 331

12.3.1 PC CRR on Non-noble Metals 331
12.3.2 PC CRR on Non-noble Metal Oxides 333
12.4 NNPE N2 Reduction Reaction (NRR) 335
12.4.1 PC NRR on Non-noble Metals 336
12.4.2 PC NRR on Non-noble Metal Oxides 336
References 338
Part III Emerging Nanomaterials for Photoelectrochemical

(PEC) Energy Conversion 341
13 2D Materials-Free Heterostructures for PEC Energy

Conversion 343
13.1 2D Materials-Free Heterostructures 343
13.1.1 PEC System for Water Splitting 343
13.1.1.1 Heterostructure as PEC Photocathodes for HER 345
13.1.1.2 Heterostructure as a PEC Photoanode for OER 348
13.1.2 PEC System for CO2 Reduction Reaction 351
13.1.2.1 Heterojunction of Semiconductors as a PEC Photocathode for CO2
Reduction Reaction 352
13.1.2.2 Non-noble Cocatalyst on Semiconductor as PEC Photocathode for CO2
Reduction Reaction 353
13.1.3 PEC System for N2 Reduction Reaction (NRR) 355
13.1.4 Challenge and Opportunities 355
References 359
14 2D-Materials-based Heterostructures for PEC Energy

Conversion 361
Bikesh Gupta, Julie Tournet, Hark H. Tan, Chennupati Jagadish, and
Siva K. Karuturi
14.1.1 Photoelectrochemical Device Configurations 362
14.1.2 Material Requirements for Photoelectrocatalysis 363
14.2 Roles of 2D Materials in Photoelectrochemical Systems 365
14.2.1 2D Materials as Photoabsorbers and Sensitizers 365
14.2.2 2D Materials as Cocatalysts 366
14.2.3 2D Materials as Electron Acceptors/Transporters 366
14.2.4 2D Materials as Protective Layers 367
14.3 Heterostructure Band Energetics at the Interface 367
14.4 2D Materials Heterostructures for Photoelectrocatalytic Redox
Reactions 369
14.4.1.1 0D/2D Heterostructures 369
Contents xi

14.4.2 CO2 Reduction Reaction 378
14.5 Challenges and Outlook 380
Acknowledgments 380
References 381
15 Polymorphic Phase Engineered Structures (PPES) for PEC

Nasir Uddin and Zongyou Yin
15.1 Photoelectrochemical (PEC) Energy Conversion 389
15.1.1 Polymorphic Phase-Engineered Structures (PPES) 389
15.2 PPES for PEC Overall Water Splitting (OWS) 389
15.2.1 PEC-OWS on Single Phases 390
15.2.2 PEC-OWS on Hetero-Phases 392
15.3 PPES for PEC Nitrogen Reduction Reaction 394
References 397
16 Rare-earth Nanomaterials for PEC Energy Conversion 399

16.1 Complex Oxides 399
16.1.1 PEC Water Splitting 399
16.1.1.1 Ln2 Ti2 O7 399
16.1.1.2 Ln2 Zr2 O7 399
16.1.1.3 Nd2 Sn2 O7 //Fe2 O3 400
16.2 Ce-Based Photoelectrocatalysts 404
16.2.1 PEC Water Splitting 404
16.2.1.1 TiO2 /Ce 404
16.2.1.2 CeO2 406
References 409
17 Non-Noble Plasmon Enhancement (NNPE) for PEC Energy

Conversion 411
Sandra Saji and Zongyou Yin
17.1 NNPE for Water Splitting 411
17.1.1 Water Splitting on Non-noble Metals 411
17.1.1.1 Ti 411
17.1.1.2 Al 412
17.1.1.3 Cu 416
17.1.1.4 Bi 421
17.1.2 Water Splitting on Non-noble Compounds 425
17.1.2.1 WO3−x 425
References 427
xii Contents
Volume 2
Part IV Emerging Nanomaterials for Photovoltaic (PV)

18 2D-Materials Free Heterostructures for Photovoltaic Energy

Conversion 431
19 2D-Materials-based Heterostructures for PV Energy

Conversion 449
Chun H. Mak, Jung-Ho Yun, Hoi Y. Chung, Yun H. Ng, and Hsien-Yi Hsu
20 Perovskite–Si Tandem Solar Cells 481

Disheng Yao and Hongxia Wang
21 III–V Compound Semiconductor Nanowire Solar Cells 531

Ziyuan Li, Hark H. Tan, Chennupati Jagadish, and Lan Fu
22 Rare-Earth Nanomaterials for PV Energy Conversion 559

23 Non-noble Plasmon Enhancement (NNPE) for PV Energy

Conversion 581
Jung-Ho Yun, Chun Hong Mak, Hsien-Yi Hsu, and Yun Hau Ng
Part V Clusters for Energy Conversion 611
24 Electrochemical Energy Conversion with Clusters 613

Zhengqing Liu, Sandra E. Saji, and Zongyou Yin
25 Photochemical Energy Conversion with Clusters 655

Xiaoshan Zhang, Sandra E. Saji, and Zongyou Yin
26 Photoelectrochemical Energy Conversion with Clusters 695

Kaili Liu and Zongyou Yin
Part VI Single Atoms for Energy Conversion 719
27 Electrochemical Energy Conversion with Single Atoms 721

Peilong Lu, Sandra E. Saji, Haitao Zhao, and Zongyou Yin
Contents xiii
28 Photochemical Energy Conversion with Single Atoms 773

Haijiao Lu and Zongyou Yin
29 Photoelectrochemical (PEC) Energy Conversion with

Single Atoms 787
Mahmoud M. Abdelnaby and Zongyou Yin
30 Future Perspectives 815

Zongyou Yin
Index 817
1
Introduction
Zongyou Yin
Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia
The rapid increase in population and economic growth brings a rise in energy
demand, which still mainly relies on natural fossil fuels, such as petroleum,
natural gases, coals, and oils, and accounts for over 70% of the total primary energy
supply. Unfortunately, this results in greenhouse gas emissions to the atmosphere.
The currently available clean H2 energy technology for emission reduction still
relies on fossil fuels to produce H2 fuel, primarily through steam methane reform-
ing at high temperatures. However, it brings with the concerns of requiring costly
high-temperature materials and emitting greenhouse gas. As widely known, the
greenhouse gases induced by global warming may seriously threaten low-lying
coastal islands and cities by rising sea levels and radically damaging homes by
extreme weather events, causing tragic habitat and economic loss. Additionally,
after seawater adsorption, greenhouse gases will accelerate ocean acidification,
threaten calcifying species in oceans, and break marine food chains, destroying
many related jobs and economies in the world. Therefore, advancing materials sci-
ence and manufacturing and developing sustainable solutions to address the energy
crisis and the global warming issue are important to global research at the current
stage, especially under the impetus of the world implementing the Paris Agreement.
In this book, multiple views from different angles were taken to present and dis-
cuss the up-to-date critical materials science and catalytic technologies for energy
conversion.
1. Four types of heavily-researched energy conversion processes/technologies, i.e.
electrochemistry, photochemistry, photoelectrochemistry, and photovoltaics, are
encompassed. They are systematically categorized in chapters and integrated
with different but logical content related to materials science and engineering to
be further addressed.
2. For each energy conversion technology, different dimensional nanomaterials,
i.e. zero-dimension (0D), one-dimension (1D), two-dimension (2D), three-
dimension (3D), clusters, and single atoms, are included and evaluated based
on their unique dimension-induced interior properties, and their merits vs.
demerits in applications.
Atomic and Nano Scale Materials for Advanced Energy Conversion, First Edition. Edited by Zongyou Yin.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
2 1 Introduction
3. Polymorphic phases of solid materials, such as crystal structural phases, single-

phase, hetero phases, and multi-phases, are discussed especially for the emerging
2D materials from the view of phase formation, control/tuning, interfacing, and
impacts on functionalities.
4. There are various functional structures, 2D-free heterojunctions, and 2D-based
heterostructures, including 2D–0D, 2D–1D, 2D–2D, and 2D–3D heterostructures,
periodic tandem, and superlattice structures combined into different energy con-
version technologies based on their effects on energy band profiles, charge trans-
port behavior, and the performance.
5. A complete comparison from materials, synthesis, reaction conditions of energy
conversion, energy conversion efficiency, and performance stability has been
made and presented in tables of the chapters, providing readers with a straightfor-
ward convenient reference for their research and/or study.
This book’s expected audiences include researchers (Master/PhD degree candi-
dates, postdoctoral fellows, research scientists, and academic staff) in academia and
academic R&D researchers and industrial technique consultants and engineers of
the related fields. The audiences with an occasional need for this book are university
lecturers, postgraduates, undergraduates, and practitioners from education institu-
tions and government funding-policy-making officials from public services of the
related fields.
With broad, significant topic coverage in energy conversion, our proposed book is
expected to bring the following benefits to the readers:
1. The brand-new forefront nano-to-atomic materials science and knowledge
enable researchers to carry out further scientific exploration.
2. Emerging energy conversion strategies as the basis enable R&D scientists/
engineers to develop modern practical energy technologies.
3. Up-to-date energy conversion science and technology provide lecturers/learners
with state-of-the-art classroom knowledge.
4. The first-hand science and technology data information helps government offi-
cials to create sustainable funding policies for their countries.
3
Part I
Emerging Nanomaterials for Electrochemical (EC) Energy

Conversion
5
2D-Materials-Free Heterostructures for EC Energy

Conversion
Kamran Dastafkan and Chuan Zhao
The University of New South Wales, School of Chemistry, Anzac Parade, Kensington, Sydney, NSW 2052,
Australia
2.1 Heterostructures for Electrochemical Water Splitting
Electrochemical water splitting is largely considered a highly efficient protocol

for energy conversion. The involved half reactions of oxygen evolution reaction
(OER) and hydrogen evolution reaction (HER), respectively, occurring at anode
and cathode are multi-electron transfer processes with sluggish charge transfer
kinetics. Therefore, an electrocatalyst is used at the electrode to decrease OER and
HER energy barriers at the electrode–electrolyte interface and increase the Faradaic
charge transfer rate [1]. A vast variety of electrocatalyst (nano)materials have been
developed to date. However, the challenges such as high energy barrier of catalyt-
ically active sites, low surface charge transfer, slow interfacial mass transport, and
poor intrinsic activity and electron conductivity still remain [2]. Heterostructured
nanomaterials, consisting of two or more interfaced catalytically active materials,
have been increasingly developed as highly efficient electrocatalysts for energy
conversion processes. Alternatively, these materials can be consisted of one electro-
chemically active phase, providing the reaction active sites, and supportive phase(s),
which augment the redox and structural properties of the main active material
[3]. In this section, we introduce various classes of metal-based heterostructured
catalysts with regard to different structures of electrocatalytically active phase,
including multicomponent heterostructures, for electrochemical water splitting
reactions. The recent advancements on the heterointerfaces in heterostructured
electrocatalysts are reviewed, as shown in Table 2.1.
2.1.1 Metal Oxide-Based Heterostructures

The surface chemistry and electrocatalytic performance of transition metal oxides
(TMOs) are hindered by the existence of a significant electrical resistance, which
limits the charge transfer for the surface Faradaic process. Constructing hetero-
junctions with other TMOs is an effective approach for optimizing the catalytic
Atomic and Nano Scale Materials for Advanced Energy Conversion, First Edition. Edited by Zongyou Yin.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
6 2 2D-Materials-Free Heterostructures for EC Energy Conversion
Table 2.1 Recent advances in nonprecious metal-based nano-heterostructured electrocatalysts for

electrochemical water splitting reactions (OER and HER).
Experimental
Heterointerfaces Electrocatalyst Application conditions Results References
Metal oxides CuCo@CuCoOx HER Support: NFa) 𝜂 10 : 112 mVc) [4]

Electrolyte: −1 d)
b: 55 mV dec
KOH 1 M
Scan rate: 2b)
OER 𝜂 10 : 190 mV
b: 88 mV dec−1
OWSe) CV10 : 1.53 Vf)
S: 100 h (at
−0.15 V)g)
Co3 O4 @CeO2 OER Electrode: RDEh) 𝜂 10 : 270 mV [5]
Electrolyte: b: 60 mV dec−1
O2 -saturated S: 10 h (at 1.6 V)
KOH 1 M
Scan rate: 5
Metal NiFe LDHs@NiO OER Electrode: NF 𝜂 10 : 210 mV [6]
hydroxides Electrolyte: b: 72 mV dec −1
KOH 1 M S: 50 h (at 50 and
Scan rate: 5 100 mA cm−2 )
Ni-BDC@Ni(OH)2 OER Electrode: GCEi) 𝜂 10 : 320 mV [7]
Electrolyte: b: 41 mV dec −1
KOH 1 M S: 20 h
Scan rate: 1
Metal pnictides FeP@Ni2 P HER Electrode: NF 𝜂 10 : 14 mV [8]
Electrolyte: b: 22.7 mV dec−1
KOH 1 M
Scan rate: 1
OER 𝜂 10 : 154 mV
b: 24.2 mV dec−1
OWS CV10 : 1.42 V
S: 40 h (at
100 mA cm−2 )
MoP@Ni2 P HER Electrode: NF 𝜂 10 : 75 mV [9]
O2 -saturated Scan rate: 5
KOH 1 M
OER 𝜂 20 : 309 mVj)
b: 77.6 mV dec−1
Scan rate: 1
OWS CV10 : 1.55 V
S: 15 h
Table 2.1 (Continued)
Experimental
Co@Ni3 N HER Electrode: CCk) 𝜂 10 : 194 mV [10]

N2 -saturated S: 24 h
KOH 1 M
OER Scan rate: 2 𝜂 10 : 307 mV
b: 57 mV dec−1
S: 24 h
Metal Ni3 S2 @MoS2 HER Electrode: CC 𝜂 10 : 173 mV [11]
chalcogenides Electrolyte: b: 39 mV dec−1
O2 -saturated S: 48 h
KOH 1 M (100 mA cm−2 )
Scan rate: 5
CoSe2 @MoSe2 HER Electrode: GCE 𝜂 10 : 218 mV [12]
N2 -saturated
KOH 1 M
Scan rate: 5
MoSSe@NiSe2 HER Electrode: NF 𝜂 10 : 69 mV [13]
H2 SO4 0.5 M
Scan rate: 0.5
Metal/Carbon Ni2 B@g-C3 N4 HER Electrode: GCE 𝜂 10 : 707 mV [14]
Electrolyte: KOH b: 221 mV dec−1
1M
Scan rate: 2
Co2 P@WC@NC HER Electrode: GCE 𝜂 10 : 91 mV [15]
H2 SO4 0.5 M S: 50 h (at
Scan rate: 5 120 mV)
Mixed-phase c-CoP@a-CoOx HER Electrode: CC 𝜂 10 : 132 mV [3]
metallic Electrolyte: KOH b: 89 mV dec−1
1M S: 24 h
Scan rate: 5
OER 𝜂 10 : 232 mV
b: 67 mV dec−1
S: 24 h
OWS CV10 : 1.66 V
S: 30 h
(continued)
Experimental
Ni3 S2 @Ni-Fe-OH OER Electrode: NF 𝜂 10 : 165 mV [16]

Electrolyte: KOH b: 93 mV dec−1
1M S: 50 h
Scan rate: 0.5 (100 mA cm−2 )
a) Ni foam.
b) In mV s−1 .
c) Overpotential.
d) Tafel slope.
e) Overall water splitting.
f) Cell voltage.
g) Stability.
h) Rotating disk electrode.
i) Glassy carbon electrode.
j) Overpotential at 20 mA cm−2 .
k) Carbon cloth.
activity of single TMOs toward OER and HER. In the recent years, developing
Mott–Schottky-type nanohybrids of non-noble metals and semiconductor oxides
has been a well-practiced strategy to make highly efficient heterostructures with
optimal intrinsic electrocatalytic activity [17].
Hou et al. prepared promoted active sites in core–shell nanowire arrays of
bimetallic CuCo- and CuCoOx -mixed oxides supported by nitrogen-doped carbon
(CuCo@CuCoOx @NC) as a Mott–Schottky hybrid catalyst for highly efficient and
stable overall water splitting [4]. The reported metal–semiconductor nanohybrid
consisted of CuCo nanoalloys and defective CuCoOx phases, synthesized as a
conductive core–shell architecture with nanowire morphology, and was shown
effective to supply a continuous electron transport between metallic and semicon-
ductor phases. CuCo@CuCoOx @NC heterostructure depicted a low overpotential
of 112 mV and Tafel slope of 55 mV dec−1 for HER and a low overpotential of
190 mV for OER, both at a current density of 10 mA cm−2 . Furthermore, a low cell
voltage of 1.53 V was needed to operate full water splitting to reach 10 mA cm−2
with a substantial stability of 100 hours. The achieved high surface conductivity
and the enlarged active surface area with abundant active sites and a continuous
electron transport remarking the efficient activity were induced by a syner-
gistic effect emerging between nanoalloy metallic, defective mixed oxide, and
heteroatom-doped carbonaceous phases.
Liu et al. [5] reported Co3 O4 @CeO2 nanohybrids made by an electron gas and
oxygen vacancy approach for advanced OER. Both metal oxides were selected based
on intrinsic properties to induce a high concentration of oxygen vacancies and an
electron-gas behavior on Ce3+ centers at the Co3 O4 –CeO2 interface. The observed
electron-gas feature acts a transport channel allowing a high charge carrier density
and a good electron conductivity for the nanohybrid catalyst. Achieving nanocube
and nanosheet morphologies for CeO2 and Co3 O4 phases, respectively, led to a
40 100
(a) Co3O4/CeO2
Current density (mA cm–2)
(b) IrO2 0.40

30 80
(c) Co3O4
(d) CeO2
jE = 1.6 v (mA cm–2)

0.32 60
Co3O4
η10(V)
20
0.24
Co3O4/CeO2
40
IrO2
(a) (b)
10
(c) 0.16 20
(d)
0
0.08 0
1.2 1.3 1.4 1.5 1.6 1.7
(a) Potential (V vs. RHE) (b)
Interface
Co3O4
e– e– e– e– e– e– e– e– e– e– e– e–
CeO2
Co3O4
CeO2
(c) (d)
Figure 2.1 (A) Polarization curves of Co3 O4 , CeO2 , and Co3 O4 @CeO2 nanohybrid and
commercial IrO2 catalysts for OER. (B) Comparisons of the obtained overpotentials of at a
current density of 10 mA cm−2 and the recorded current densities at a potential of 1.6 V.
(C) Schematic representation of the interfacial electronic structure in Co3 O4 @CeO2
nanohybrid. (D) High-angle annular dark-field (HAADF). Image of Co3 O4 @CeO2 nanohybrid.
Source: Reprinted with permission from Liu et al. [5]. Copyright 2019, Wiley.
remarkable OER performance with a low overpotential of 270 mV at a current

density of 10 mA cm−2 and a high turnover frequency (TOF) of 0.25 s−1 compared
with pure CeO2 and Co3 O4 phases and also outperformed the benchmark IrO2
catalyst (Figure 2.1).
2.1.2 Metal Hydroxide-Based Heterostructures

Transition metal-based hydroxides (TMOHs) are commonly known as highly active
materials for anodic OER process of water electrolysis. Currently, NiFe-based
binary systems including NiFe-mixed hydroxides (NiFe(OH)x ) and NiFe-layered
double hydroxides (NiFe LDHs) are recognized as noble-metal-free benchmark
OER-catalyzing heterogeneous catalysts [18]. In the recent years, tremendous
efforts have been dedicated to increase the efficiency of TMOH catalyst by different
strategies, i.e. precise/systematic metal doping, ternary hydroxide formation with
another transition metal, surface active site modification, and heterostructuring

[19].
Sirisomboonchai et al. fabricated core–shell heterostructure catalysts consisting
of binary NiFe LDHs decorated on hierarchical NiO microflakes (NiFe LDHs@NiO)
through a two-step hydrothermal/post-thermal annealing procedure for efficient
OER [6]. The developed architecture achieved a low overpotential of 265 mV
affording 10 mA cm−2 current density due to the well-established composite
microstructure with strong interface connection and interfacial interactions that
facilitated electron transfer between catalyst surface and Ni foam as current collec-
tor. At the same time, porous core–shell array morphology substantially improved
the contact surface between composite catalyst and hydroxyl reactants in the
alkaline KOH electrolyte, where the interlayer NiO phase between NiFe LDHs and
Ni foam substrate acts as a mediator for effective electron transport to Ni foam. The
outer ultrathin Nife LDH nanosheets also were well-wrapped over NiO microflakes,
maximizing the active site exposure to hydroxyl species. Moreover, the observed
apparent activity of NiFe LDHs@NiO was even furthered through in situ inter-
calating NiFe LDH nanoarrays in formamide organic solvent at 30 ∘ C for just five
minutes through an ultrasound treatment. This resulted in promoted ionic transport
and gas diffusion channels within the LDH slabs. The treated NiFe LDHs@NiO
heterostructure then exhibited stable high current densities of 50 and 100 mA cm−2
for 50 hours and a significantly reduced overpotential for 10 mA cm−2 to 210 mV.
It was discussed that NiO in the intercalated composite catalyst effectively facili-
tated the cleavage of HO—H bond and the subsequent conversion of the adsorbed
OH species to molecular oxygen. NiFe LDHs with extended interlayer spaces also
supplied abundant exposed active sites and highly increased mass transfer routes
for ion diffusion/electron transfer at the catalyst–electrolyte interface.
Zhu et al. [7] described the utilization of a heterostructured Ni-based metal–
organic framework (Ni–MOF) and Ni hydroxide for efficient OER, owing to the
inherent features of extended surface with coordinatively unsaturated metal species
and fast mass transport of MOFs and innate electrocatalytic activity of Ni(OH)2 .
One common problem of using MOFs as catalyst materials is their relatively
fast autonomous aggregation rate that can be obviated through the formation of
nano-heterointerfaces with TMOs and TMOHs. The developed Ni-BDC@Ni(OH)2
(BDC: 1,4-benzenedicarboxylate, C8 H4 O4 ) hybrid nanosheets were synthesized
by a sonication-assisted solution method. While the large surface area of Ni-BDC
MOF was maintained, coupling with Ni(OH)2 significantly improved the electronic
structure of Ni atoms in Ni(OH)2 phase, which effectively resulted in a high
density of Ni sites with high oxidation states as OER main active sites. As a result,
Ni-BDC@Ni(OH)2 revealed 5.5 and 20.6 times higher activity (82.5 mA cm−2 ) at
1.6 V vs. reversible hydrogen electrode (RHE) than those of uncoupled Ni-BDC
(15.1 mA cm−2 ) and Ni(OH)2 (4.0 mA cm−2 ), respectively.
2.1.3 Metal Pnictide-Based Heterostructures

Coordinating transition metal phosphides (TMPs) or nitrides with each other or
other transition metals in one structure has been noted as a rational design strategy
that supplies augmented density of the surface active sites and interfacial electron
conductivity [20]. In particular, bimetallic TMPs have been studied in much details,
owing to their superior performance with respect to monometallic phosphide
catalysts [21]. Phosphorous atom is widely recognized as an efficient entity for the
non-noble metal catalysts for alkaline HER, mostly regarding its innate charac-
teristic as a good proton acceptor that can attenuate the metal–hydrogen bonding
strength and accelerate the hydrogen desorption during the HER [22].
Yu et al. synthesized porous hybrid iron–di-nickel phosphides (FeP@Ni2 P) sup-
ported on commercial Ni foam as a high-performance bifunctional material for over-
all water splitting in alkaline media [8]. This hybrid was highly efficient toward both
OER and HER with a Pt-like performance (−14 mV overpotential at −10 mA cm−2 )
and a superior activity than IrO2 (154 mV overpotential at 10 mA cm−2 ). As a bifunc-
tional catalyst, FeP@Ni2 P required only 1.42 V cell voltage to deliver 10 mA cm−2
and 1.72 V achieving a practical current density of 500 mA cm−2 for industrial
considerations. Excellent durability of 40 hours at 500 mA cm−2 corroborated this
bifunctional hybrid catalyst, outperforming the current industrial benchmark
materials that require 2.40 V to produce 400 mA cm−2 .
Du et al. [9] prepared hierarchical MoP@Ni2 P heterostructures on Ni foam sub-
strate as a bifunctional catalyst for operating HER and OER. Through an in situ con-
trollable hydrothermal-phosphidation process, MoP@Ni2 P was made with optimal
electrocatalytic properties emerging from their unique hierarchical heterostructures
and collaborative interactions of the bimetallic phosphides. The proposed bifunc-
tional MoP@Ni2 P@NF electrode required a low cell voltage of 1.55 V to deliver a
current density of 10 mA cm−2 in alkaline media (Figure 2.2).
Zhu et al. [10] reported in situ grown epitaxial heterojunction as effective strategy
to make high-performance nitride-based materials for electrochemical water split-
ting. Arrays of Co@Ni3 N nanowires were prepared by an atomic epitaxial in-growth
method with a nanoconfinement effect to augment the interface properties. Surface
nano-heterojunction engineering and fine-tuning the interface electronic structure
were all carried out by a thermal annealing process on NiCo2 O4 spinel precursor
under optimized conditions with a precise control over morphology. This in situ
in-growth strategy at nanometric scale promoted the electron transfer between two
different domains of the epitaxial interface and resulted in a significant increase in
the intrinsic activity for both HER and OER. Almost 15 and 19 times larger elec-
trocatalytic TOFs were achieved for the hybrid Co@Ni3 N nanowires with respect
to the pure Ni3 N nanorods for HER and OER, respectively. The nanoconfinement
effect between metallic Co and Ni3 N nanowires caused electronic binding energy
shift and highly boosted the Faradaic charge transfer across the Co–Ni3 N interface.
2.1.4 Metal Chalcogenide-Based Heterostructures

Strong interfacial interactions and electronic coupling effect have also been
observed when hybridizing two or more transition metal chalcogenides, i.e. sul-
fides, selenides, and tellurides [23]. Such chalcogenide-based heterocatalysts can
further improve the electrocatalytic performance of individual metal chalcogenides
or the corresponding metallic catalysts through optimizing electronic structure at
(a)
Hydrothermal In situ
in situ growth phosphorization
Ni Mo-based precursor MoP

Ni2P
(b) (c)
MoP layers
0.5 nm
Ni2P (100)
5 um
MoP nanoflowers Ni2P nanoparticles
0.22 nm
Ni2P (111)
0.32 nm
MoP (001)
SE 5 nm
3 um
(d) 300 MoP/Ni2P/NF (e) MoP/Ni2P/NF
RuO2/NF 0 Pt/C/NF
250 Mo-based/NF precursor Mo-based/NF precursor
Ni foam
200
Ni foam –30
j (mA cm−2)
j (mA cm−2)
150 –60
100 –90
50
–120
0
–150
1.2 1.3 1.4 1.5 1.6 1.7 1.8 –0.6 –0.5 –0.4 –0.3 –0.2 –0.1 0.0
Potential (V vs. RHE) Potential (V vs. RHE)
Figure 2.2 (a) Schematic illustration of the synthesis of MoP@Ni2 P heterostructures.

(b) Scanning electron microscopy (SEM) and (c) HRTEM images of MoP@Ni2 P
heterostructures. Comparison of linear sweep voltammetry (LSV) polarization curves of
MoP@Ni2 P heterostructures for (d) OER and (e) HER. Source: Reprinted with permission
from Du et al. [9]. Copyright 2017, Royal Society of Chemistry.
their interface while at the same time benefiting from various morphologies of the
coupled phases.
Wang et al. [11] described an asymmetric electrode design for alkaline water split-
ting consisting of bimetallic disulfide heterostructures as cathode (Ni3 S2 @MoS2 )
and the same heterostructure hybridized with a superficial amorphous bimetal-
lic hydroxide phase as anode (Ni3 S2 @MoS2 @NiFe(OH)x ) to operate efficient
HER and OER reactions, respectively. An optimized hydro/solvothermal process
assisted by an electrodeposition step was adapted to allow the in situ growth of the
(bi)-transition metal disulfides (TMDSs) and mixed hydroxides. The obtained cath-
ode and anode exhibited a first-rate activity and promoted electrolysis durability.
The cathode, Ni3 S2 @MoS2 , showed an overpotential of 173 mV at −100 mA cm−2
for HER, and the anode, Ni3 S2 @MoS2 @NiFe(OH)x , demonstrated an overpotential
of 309 mV at the same current density. Tight interstratification among the TMDS
nanosheet arrays and the amorphous bimetallic hydroxides resulted in augmented
intermediate (OH− /H+ ) adsorption, electron conductivity, charge transfer, and
enhanced surface active sites. A two-electrode alkaline water electrolyzer was
developed by the proposed cathode and anode, which exhibited low overall cell
voltages of 1.55 and 1.71 V to deliver current densities of 10 and 100 mA cm−2 ,
respectively.
Zhao et al. [12] synthesized Co,Mo-based transition metal diselenide (TMDSe)
heterostructures with dense water adsorption/dissociation active sites for efficient
alkaline HER. Usually, TMDSe materials are suitable electrocatalysts for HER in
acidic media but provide weak performance in alkaline electrolytes, because of
the highly sluggish water dissociation kinetics. The proposed heterostructure with
CoSe2 quantum dots anchored on MoSe2 nanosheets (CoSe2 @MoSe2 ) increased
the water adsorption sites due to the CoSe2 incorporation on the basal planes of
MoSe2 to promote water dissociation. As a result, the CoSe2 @MoSe2 heterostruc-
ture exhibited advanced HER in 1 M KOH with an overpotential of 218 mV to
produce a current density of 10 mA cm−2 , which is more than 100 mV and nearly
200 mV smaller than the required overpotential values for single CoSe2 and MoSe2
phases, respectively. It was suggested that the water adsorption and the subsequent
dissociation process were expedited significantly due to the enriched edge site
CoSe2 phase and the populated adsorption combination sites for H* intermediate
on MoSe2 phase.
Zhou et al. reported accelerated HER activity and kinetics on a ternary chalco-
genide structure consisting of Mo-mixed sulfoselenide particles combined with a
self-supporting porous Ni diselenide [13]. Through a facile two-step selenization
process at moderate temperature (600 ∘ C) with subsequent in situ growth of
MoSSe vertical layers, the ternary MoSSe@NiSe2 catalyst was synthesized on
three-dimensional (3D) Ni foam scaffold. The advantages of the TMDSe developed
heterostructure are high conductivity, double-gyroid structure (3D, porous, and
large density of exposed edge sites), and the emergence of catalytic synergy between
the TMDSe phases. As a result, a low overpotential of 69 mV was obtained to achieve
a current density of −10 mA cm−2 in 0.5 M H2 SO4 electrolyte compared with the
high overpotentials of 118 and 153 mV needed for the binary MoS2 phase on NiSe2
self-supported foam and the single NiSe2 foam, respectively. A low Tafel slope of
42.1 mV dec−1 exhibited advanced Tafel mechanism for hydrogen desorption on
MoSSe@NiSe2 heterostructure during HER that was much lower than Tafel slopes
of binary MoS2 (58.5 mV dec−1 ) and pristine NiSe2 (46.4 mV dec−1 ) phases. Also, no
obvious degradation of cathodic current densities was observed for the developed
TMDSe heterostructure after 1000 continuous CV cycles (Figure 2.3).
(a)
Selenization (NH4)2MoS4
in Ar gas modification
600 °C Selenization
at 500 °C
3D porous 3D porous
3D Ni foam
NiSe2 foam MoSSe/NiSe2 foam
(b) (c)
(d) 0 0 (e) 0.28 –1 –2

Slope = 46.4 mV dec , j0 = 11.4 μA cm
–2 –1 –2
Slope = 58.5 mV dec , j0 = 104.9 μA cm
–20 –1 –2
–4 0.21 Slope = 42.1 mV dec , j0 = 299.4 μA cm
Overpotential (V)
–6
–40 –8
0.14
–10
–60 –0.16 –0.12 –0.08 –0.04 –0.00
Potential (V vs. RHE)
Pure Nise2 foam 0.07
–80 MoS2/Nise2
MoS2(1–x)Se2x/Nise2
Pt wire 0.00 –1 –2
Pt: 30 mV dec , 1.078 mA cm
–100
–0.6 –0.5 –0.4 –0.3 –0.2 –0.1 0.0 –0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Potential (V vs. RHE) Log│j (mA cm–2)│
(f) (g)
16
Cdl = 319.15 mF cm–2
Δj0.15 V vs. RHE (mA cm–2)
0
14
–100 Pure Nise2 foam
12 MoS2/Nise2 foam
–200 10 MoS2(1–x)Se2x/Nise2
–300 8 Cdl = 30.88 mF cm–2

–400 Initial
6 Cdl = 7.48 mF cm–2
After 1000 cycles 4
–500
After 1000 cycles 2
and stability test
–600
0
–0.20 –0.15 –0.10 –0.05 –0.00 0 20 40 60 80 100120140160180200
Potential (V vs. RHE) Scan rate (mV s–1)
Figure 2.3 (a) Schematic growing process of ternary MoS2(1−x) Se2x particles on porous
NiSe2 foam. (b, c) Typical SEM and transmission electron microscopy (TEM) images of the
grown ternary MoS2(1−x) Se2x particles on porous NiSe2 foam. (Scale bar: SEM, 1 μm; TEM,
5 nm.) (d) Comparison of the polarization curves of MoS2(1−x) Se2x @NiSe2 and MoS2 /NiSe2
hybrid catalysts with pure NiSe2 and Pt wire electrodes for HER and (e) the corresponding
Tafel plots. (f) Polarization curves of the as-prepared ternary MoS2(1−x) Se2x @NiSe2 hybrid
electrodes after 1000 CV cycles and after the stability test. (g) Extracted C dl values for pure
NiSe2 , MoS2(1−x) Se2x @NiSe2 , and MoS2 /NiSe2 hybrid catalysts. Source: Reprinted with
permission from Zhou et al. [13]. Copyright 2016, Nature publications.
2.1.5 Metal/Carbon-Based Heterostructures

As a main challenge for the electrocatalytic water splitting, multi-electron and
multi-charge transfer processes with slow kinetics, hinder the efficiency of HER
and OER reactions. To tackle this issue, an interesting approach is to design new
(multi)phase architectures with exposed active sites and accelerated charge transfer
kinetics [18e, 24]. The diffusion path for ionic reactants, i.e. OH− /H+ for alka-
line/acidic water splitting, respectively, can be shortened using one-dimensional
building blocks for constructing 3D hetero-hierarchical structures [25]. The contact
between the exposed surface and electrolyte can be largely increased to afford
superior Faradaic electron transfer. For example, as a binary TMO, spinel copper
cobaltite has intrinsically promising electrocatalytic activity and rate capability that
arise from inter-metallic synergy between Cu and Co. When hybridizing CuCoO4
with carbon quantum dots (CuCoO4 @CQDs), the restrictions of low electrical
conductivity and performance robustness were significantly resolved [26]. The
surface of carbon quantum dots (CQDs) with rich negative charges facilitates the
electrostatic interactions with TMOs with positively charged surface.
Cao et al. showed the enhancement in HER activity by establishing hetero-
junction between Ni boride and graphitic carbon nitride (Ni2 B@g-C3 N4 ) [14].
Particularly, owing to its function as a good semiconductor, g-C3 N4 is used in the
energy conversion research. Through a facile process of directly heating the N-rich
urea as precursor in a semi-closed environment and post-thermal calcination,
Ni2 B nanoparticles were encapsulated into g-C3 N4 bulk layers. As a result, highly
enlarged specific surface area, exfoliation of these layers, and promoted electronic
conductivity were achieved by heterostructuring these metal/carbon phases.
The prepared composite catalyst demonstrated an improved onset overpotential
of 300 mV, a Tafel slope of 221 mV dec−1 , and an overpotential of 707 mV at
10 mA cm−2 with respect to the original g-C3 N4 material.
Gao et al. constructed a nano-heterojunction between cobalt phosphide and
tungsten carbide structures that were covered with nitrogen-doped carbon through
a one-step annealing treatment of the corresponding polyoxometalate struc-
tures Na9 (NH4 )5 [{(B-α-PW9 O34 )Co3 (OH)(H2 O)2 (Ale)}2 Co]⋅35H2 O (Co7 P6 W18 ) and
dicyandiamide (DCA). Also, they demonstrated a highly efficient HER perfor-
mance for the resulted heterostructure (Co2 P@WC@NC) [15]. Conducting cobalt
phosphorization and tungsten carbonization steps at the same time in a confined
space made an isolated Co2 P@WC nano-heterojunction phase. The developed
heterostructure exhibited advanced hydrogen electrocatalysis with a small over-
potential of 91 mV to afford a current density of −10 mA cm−2 in acidic media,
a small Tafel slope of 40 mV dec−1 (remarking a Tafel mechanistic pathway for
the molecular hydrogen desorption from the catalyst surface), and an excellent
long-term stability for 50 hours at an overpotential of 120 mV. It was revealed that
the facilitated HER kinetics ensued from the emerging synergistic interactions
between Co2 P, WC, and pyridinic NC phases in the heterostructure. The proposed
hybrid catalyst also showed favorable HER performances in other media with
neutral and alkaline pH values.
2.1.6 Mixed-Phase Metallic Heterostructures

Heterostructuring with tenacious interfacial interactions between different struc-
tures of transition metal-based catalysts, i.e. oxides, hydroxides, chalcogenides, pnic-
tides, and also conductive (nano)carbons, is also a viable approach to enable catalytic
synergy and to improve electron transfer kinetics among these OER- and HER-active
materials [27].
Yu et al. synthesized crystalline CoP nanoparticles embedded in amorphous CoOx
nanoplates through a combined solvothermal low-temperature phosphidation pro-
cedure [3]. The designed c-CoP@a-CoOx hybrid catalyst presented a remarkable
bifunctional performance for alkaline water splitting, and the authors attributed this
bifunctionality to the established catalytic synergy between Co phosphide and oxide
phases. The coupling of crystalline CoP and amorphous CoOx phases constructed
a hybrid matrix with well-formed phase boundary and an electronically improved
nanointerface with synergistic effect between the Co phases. As a result, the pro-
posed Co-based heterostructure showed advanced OER and HER activities com-
pared with the corresponding benchmark, IrO2 and Pt/C catalysts. In addition, an
efficient and stable overall water splitting performance was achieved by applying the
c-CoP@a-CoOx heterostructure as both anode and cathode in alkaline media where
a low cell voltage of 1.66 V was obtained to deliver a current density of 10 mA cm−2
with good stability for 30 hours.
Zhang et al. [28] constructed Mo phosphide-multiwalled carbon nanotubes
(MoP@MWCNT) hybrid catalyst with efficient HER activity over the entire pH
range in electrolytes. While MoP is generally recognized for its intrinsic HER
activity, making the well-formed MoP fine nanostructures with fully exposed
edge sites, in contrast to the dominant basal sites, along with enlarged surface
active sites is a challenging task. However, hybridizing the crystalline MoP with
carbonaceous phases such as carbon nanotubes (CNTs) is a feasible approach
to increase the intrinsic activity of MoP. A two-step synthesis procedure involv-
ing wet chemical route coupled with gas–solid phosphorization was utilized to
transform the MoOx (OH)y @MWCNT intermediate structure to MoP@MWCNT
catalyst. The proposed hybrid structure contains fine MoP nanoparticles, uniformly
distributed on the sidewalls of CNTs and exhibiting highly active and stable HER
performance in all pH-value media. Low overpotentials of 83, 102, and 86 mV
were obtained for MoP@MWCNT heterostructure to deliver a current density of
−10 mA cm−2 in acidic (0.5 M H2 SO4 ), neutral (1 M phosphate buffer), and alkaline
(1 M KOH) electrolytes. Furthermore, the achieved overpotentials were stable for
continuous HER process of 40 hours. The well-crystallized texture of the anchored
MoP nanoparticles over MWCNTs was described to significantly influence the
intrinsic activity. Besides, the incorporation of MWCNTs significantly decreased
the rate of aggregation and sintering of MoP nanocrystals during the synthesis
and also enhanced the electrical conductivity and electronic interactions with the
small-sized crystalline MoP phase.
Zou et al. [16] reported an ultrafast method to form nickel sulfide nanosheet
arrays, coated with amorphous NiFe binary hydroxides (Ni3 S2 @Ni–Fe–OH) and
supported on Ni foam scaffold as a composite catalyst for efficient OER at high

current densities. The hybrid Ni3 S2 @Ni–Fe–OH catalyst was grown in situ atop of
Ni foam through a fast and facile interface interaction derived by the immersion of
hydrothermally synthesized Ni foam-supported Ni3 S2 into an iron cationic solution
at 100 ∘ C for five seconds. The integration of binary NiFe hydroxide layer with
highly intrinsically active sites and the conductive and stable nanoarrays of Ni
sulfide phase allowed for highly boosted catalytic activity in both 1 M KOH and
concentrated (30%) KOH electrolyte and resulted in high structural robustness,
electronic conductivity, and strong coupled interface between the hydroxide and
sulfide phases. Ni3 S2 @Ni–Fe–OH heterostructure demonstrated almost 3 and 2.5
times higher activity with respect to the uncoupled Ni3 S2 phase and also IrO2
benchmark OER catalyst at high current densities. Particularly, this delivered
current densities of 10 and 100 mA cm−2 with overpotentials of 165 and 300 mV
in 1 M KOH and high current density of 1000 mA cm−2 with an overpotential of
479 mV in 30% KOH. Stable performance for continuous OER of 50 hours was
observed at various current densities of 100, 500, and 1000 mA cm−2 (Figure 2.4).
2.1.7 Multicomponent Metal-Based Heterostructures

In practice, various interphasic incorporations between catalytically active and
supporting phases exist in multicomponent heterostructure where the overall
surface and interface properties are boosted to outperform the single-component
catalysts. The most important aspects of such improved functionality include the
enhancement in (i) electrochemically surface area and number of active sites;
(ii) extent of exposure of surface active sites to electrolyte; (iii) intrinsic activity of
the catalytically active phase(s) through augmented interaction with the interfacial
intermediates; (iv) surface and interface features such as electron conductivity,
charge transfer, and mass transport; (v) morphology and nanoarray-based surfaces
such as core–shell, sandwich, and multidimensional structures; (vi) the elec-
trocatalytic synergy between interfaced structures; and (vii) in situ phenomena
during the electrocatalysis such as catalyst surface reconstruction and electron
redistribution that could positively affect the dynamic stability and activation of
active phase(s) and further modulation of the catalyst electronic structure [29].
Here, we introduce recent advances on multicomponent heterostructured catalyst
materials for electrochemical water splitting (Table 2.2).
2.1.7.1 Metal Oxide-Based Multicomponent Heterostructures

2.1.7.1.1 Transition Metal/Metal Oxide Heterointerfaces
TMOs and hydroxides are among the most studied electrocatalysts for water split-
ting reactions. The main consideration for the development of the corresponding
multicomponent heterostructures is the modulation of their structure, composition,
and morphology with respect to the interfaced components [37]. The typical and
main TMOs involve mono- and bimetallic oxides, mixed (hydro)oxides, spinel
oxides, and perovskites along with layered structures, i.e. LDHs [38]. Incorporation
of water adsorption/dissociation centers based on TMOs has been an effective
(a)
5s
100 °C
H2O
FeCl3.6H2O
Ni3S2@NF Ni–Fe–OH@Ni3S2@NF
(b) (c)
(d) 1000 20 (e) 2.0

900 IrO2
15
)
Ni–Fe–OH@Ni3S2/NF
–1
1.9
800
cm
10 100 mA cm–2
700
j (mA
5
j (mA cm–2)
600 1.8 500 mA cm–2

0
500 1.25 1.30 1.35 1.40 1.45 1.50 1.55
1.7
400 NF
300 IrO2
1.6
200 Ni3S2/NF 100 mA cm–2
100 Ni+ – Fe–OH@Ni3S2/NF 1.5
0
1.4
1.3 1.4 1.5 1.6 1.7 1.8 0 5 10 15 20 25 30 35 40 45 50
Potential (V vs. RHE) Time (h)
(f) 3.5 (g)
–
OH
3.0 Amorphous
Ni–Fe–OH O2
2.5
2.0 1000 mA cm–2 Ni3S2
1.5
1.0 Electron
highway
0.5
Ni foam
0.0
0 5 10 15 20 25 30 35 40 45 50
Time (h)
Figure 2.4 (a) Schematic preparation of Ni–Fe–OH@Ni3 S2 @NF by quickly immersing

Ni3 S2 @NF in a preheated aqueous solution with Fe3+ ions at 100 ∘ C for five seconds.
(b, c) Typical SEM of Ni3 S2 @NF and Ni–Fe–OH@Ni3 S2 @NF. (d) LSV curves of
Ni–Fe–OH@Ni3 S2 @NF (black), Ni3 S2 @NF (gray), IrO2 (light gray), and Ni foam (dash line)
for OER in 1 M KOH. (e) Chronopotentiometric curves of Ni–Fe–OH@Ni3 S2 @NF (black) and
IrO2 (light gray) in 1 M KOH. (f) Chronopotentiometric curve of Ni–Fe–OH@Ni3 S2 @NF in
30 wt% KOH with a current density of 1 A cm−2 . (g) Schematic illustration of the OER
activity enhancement using Ni–Fe–OH@Ni3 S2 @NF heterostructure. Source: Reprinted
with permission from Zou et al. [16]. Copyright 2017, Wiley.
Table 2.2 Recent advances in nonprecious metal-based multicomponent nano-heterostructured

electrocatalysts for electrochemical water splitting reactions (OER and HER).
Appli- Experimental Reference

Heterointerfaces Electrocatalyst cation conditions Results no.
Metal/metal Co3 O4 @CoO@Co OER Support: RDE Eonset : 1.58 V [30]

oxide Electrolyte: b: 73.3 mV dec −1
KOH 1 M S: 15 h
Scan rate: 5 (at 1.58 V)
FeOOH@Co@FeOOH OER Electrode: NF 𝜂 20 : 250 mV [31]
Electrolyte: b: 32.0 mV dec −1
NaOH 1 M S: 50 h a)
Scan rate: 5
Metal/metal Co@CoOx @N,O,S-C HER Electrode: NF 𝜂 10 : 61 mV [32]
oxide/nonmetal Electrolyte: b: 78 mV dec−1
KOH 1 M S: 20 h
Scan rate: 2 (at 10 mA cm−2 )
Co3 O4−x @C@Fe2−y Coy O3 OER Electrode: RDE Eonset : 1.52 V [33]
Electrolyte: 𝜂 10 : 350 mV
KOH 1 M
b: 37.6 mV dec−1
Scan rate: 5
Metal Co9 S8 @Zn0.8 Co0.2 S@C OER Electrode: GCE 𝜂 10 : 292 mV [23h]
non-oxide/ Electrolyte: b: 52 mV dec −1
nonmetal KOH 0.1 M S: 6 h (at 1.58 V)
Scan rate: 10
NiP@NiFeP@NP-C HER Electrode: RDE 𝜂 10 : 238 mV [34]
KOH 1 M
OER 𝜂 10 : 250 mV
Scan rate: 1
b: 58 mV dec−1
OWS CV10 : 1.53 V
S: 20 h (at
100 mA cm−2 )
CoP@MoS2 @CNTs HER Electrode: GCE 𝜂 10 : 12 mV [35]
H2 SO4 0.5 M S: 60 000 s
Scan rate: 5 (at 50 mV)
Metal CoS@β-Co(OH)2 @MoS2+x OWS Electrode: NF 𝜂 10 : 350 mV [36]
oxide/metallic Electrolyte: S: 100 000 s
non-oxide KOH 0.1 M (at 10 mA cm−2 )
Scan rate: 2
a) Long-term stability recorded at current densities of 20, 50, 100, and 200 mA cm−2 .
approach to design OER/HER catalyst during the past decade. For example, a
cobalt-based porous nanocomposite OER catalyst was developed based on Co2+
oxide and Co2+,3+ mixed oxide phases (Co3 O4 @CoO@Co) that were exposed on a
carbon shell [30]. An interesting interface is evolved between TMOs and transition
metals that efficiently favor HER. For example, it was reported that the in situ
deposited MnO2 @NiO@Ni heterostructure, self-supported by a Ni foam substrate
via hydrothermal reaction, possesses multiple metal–metal oxide interfaces favoring
hydrogen adsorption and HER kinetics closely over those usually observed for the
commercial Pt/C catalyst [39].
Another highly active TMO-based active phase in multicomponent het-
erostructures is transition metal oxyhydroxides (TMOOHs) that have been a
characteristic type of OER electrocatalysts during the past years. For example,
FeOOH@Co@FeOOH heterostructure was reported with tubular nanoarray
morphology (Figure 2.5) [31]. Metallic Co sandwiched by FeOOH phases was
utilized as a conductive core for the electron flow and transmission throughout
the heterostructure network, which effectively boosted the electrical conductivity.
Also, the emerged electronic interaction between Co and FeOOH phases highly
contributed to the decreased interface barrier for the adsorption energies of oxy-
genated intermediates. As a result, FeOOH@Co@FeOOH hybrid catalyst exhibited
a low overpotential of 250 mV at a current density of 21 mA cm−2 and a long-term
stability of 50 hours at a high current density of 200 mA cm−2 .
2.1.7.1.2 Transition Metal/Metal Oxide/Nonmetal Heterointerfaces

Due to their interface rational design with control over morphology and size in
hybrid systems, the integration of metal, metal oxide, and nonmetal phases is an
appealing strategy [40]. Specifically, the use of nonmetal phases, i.e. (nano)carbon
materials, guarantees the electron conductivity and active site exposure but
Ni foam (NF) ZnO–NF ZnO@Co–NF Figure 2.5 Fabrication

ZnO process of
Co metal FeOOH@Co@FeOOH-NF
FeOOH electrocatalysts. Source:
Reprinted with permission
from Feng et al. [31].
ZnO Co Copyright 2016, Wiley.
Electro- Electro-
deposition deposition
ZnO
FeOOH/C/FeOOH removal
HNT
FeOOH
superhighway
interaction
Electronic
Electron
Electro-
deposition
FeOOH/C/FeOOH HNTAs–NF Co NTAs-NF

at the same time is influential in the interphasic electronic interactions [41].

For example, Zhang et al. synthesized a multicomponent Co-based HER cat-
alyst by pyrolyzing filter paper as the carbon source and a moderate Co ionic
adsorption (Co@CoOx @N,O,S–C) [32]. Encapsulated Co@CoOx nanoparticles
in N,O,S-tri-doped 3D porous carbon network, where dopants were supplied by
the hydroxyl-enriched cellulose in the filter paper and the adsorbed thiourea,
provided strong intercoupling electronic interactions. Benefiting from the porosity
and electron conductivity of doped carbon, the robust Co@CoOx @N,O,S–C het-
erostructure showed a small overpotential of 61 mV at −10 mA cm−2 , a small Tafel
slope of 78 mV dec−1 , and a high stability for 2000 cyclic voltammetry cycles in
1 M KOH.
The metal oxide/nonmetallic heterointerfacing is also promising technique for
OER. Xu et al. [33] fabricated Co3 O4−x @C@Fe2−y Coy O3 heterostructure via a
two-step synthesis procedure consisting of the thermal treatment of a zeolitic imi-
dazolate framework (ZIF-67) precursor followed by a solution-phase self-assembly
growth of Fe2−y Coy O3 phase on the defect-rich bulk Co3 O4 phase (Figure 2.6).
A precise control on atomic ratios in metal and metal oxide phases in the developed
hybrid system allowed for various structural properties including the emergence of
polyhedron (Co3 O4−x @C), nanoparticle (bulk Co3 O4 ) and nanowire (Fe2−y Coy O3 )
morphologies, surface oxygen vacancies, expanded surface area, and reinforced
interfacial electronic coupling between different phases that provide catalytic
synergy for the heterostructure. The reported multicomponent catalyst was highly
efficient for OER and exhibited lower overpotential (290 mV) and higher current
density (70 mA cm−2 at 1.7 V vs. RHE) with respect to Co3 O4−x @carbon and pure
Co3 O4 phases.
100
90 Co3O4–x–C@
80
Fe2–yCoyO3
j (mA cm–2)
70
60
50 Co3O4–x-C
40
30
Fe2–yCoyO3
20
10
0
1.3 1.4 1.5 1.6 1.7
E (V vs. RHE)
1.80
1.77
92.9 mV dec–1
1.74
1.71
E (V)
1.68
1.65 74.3 mV dec–1
1.62
1.59
1.56
37.6 mV dec–1
1.53
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Log j
Figure 2.6 Fabrication process and OER activity of (a) Co3 O4−x @C@Fe2−y Coy O3
heterostructures. Source: Reproduced from Xu et al. [33]. Copyright 2017, American
Chemical Society.
2.1.7.2 Metal Non-oxide-Based Multicomponent Heterostructures

2.1.7.2.1 Transition Metal Non-oxide/Nonmetal Heterointerfaces
Similar to normal heterostructures, transition metal chalcogenides (sulfides,
selenides, and tellurides) and pnictides (nitrides and phosphides) can greatly
contribute to the overall activity delivered by multicomponent heterostructures.
The most highlighted feature offered by using metallic non-oxide active phases is
the intensified chemical and electronic coupling interactions with other non-oxide
or nonmetal phases, leading to the overall improved performance of the het-
erostructure [42]. Promising multicomponent systems can be developed by metallic
non-oxide carbonaceous heterointerfaces, where the active site accessibility (i.e.
edge/corner sites) and electron/ion transport are greatly increased due to the
confinement effect of (nano)carbon framework [43]. For example, Chen et al. [23h]
studied the electronic coupling at an atomic level nanointerface between Co9 S8
and Co-doped ZnS structures and the corresponding hybrid catalyst with another
interface with porous carbon polyhedral (Co9 S8 @Zn0.8 Co0.2 S@C). The constructed
heterostructure revealed an overpotential of 292 mV to deliver a current density of
10 mA cm−2 for OER along with a Tafel slope of 52 mV dec−1 , which was superior
to those observed for IrO2 /C catalyst. Furthermore, an energetically favored local
coordination environment was ascribed to Co9 S8 @Zn0.8 Co0.2 S@C heterostructure
by accelerating the charge transport over the exposed active sites.
TMPs with expedited electron transfer from metal center to the more electroneg-
ative phosphorous atom provide better charge density over phosphorous atoms
and charge separation over the active surface in multicomponent heterostruc-
tures [38a, 44]. Accordingly, faster adsorption and interaction with OER/HER
intermediate species occur by developing TMP–TMP or TMP–C heterointerfaces.
For instance, Weng et al. [34] designed a novel synthesis approach based on a 3D
metal–organic open framework, composed of phosphine, pyridine, and thiocyanate
organic linkers acting as the source of both transition metals and heteroatoms,
to prepare heteroatom-doped carbon-encapsulated metal phosphides as efficient
bifunctional hybrid electrocatalysts for water splitting. A dual anodic and cathodic
catalyst was fabricated based on the 3D-MOF-derived interfaced metal phosphide
nanoparticles in (N,P)-co-doped carbon network (NiP@NiFeP@NP-C) for OER and
HER reactions in alkaline media. A two-electrode alkaline water electrolyzer was
also fabricated using the MOF-derived NiP@NiFeP@NP-C heterostructure that
produced 10 and 100 mA cm−2 at low cell voltages of 1.53 and 1.68 V, respectively.
Mixed-phase non-oxide metal-based multicomponent catalysts can bene-
fit from a wide range of innate properties of these materials. Pan et al. [35]
described a Pt-approaching HER activity for a heterostructure composed of cobalt
phosphide and molybdenum sulfide together anchored on carbon nanotubes
(CoP@MoS2 @CNTs). An in situ growth synthesis process was adapted to grow CoP
nanorods on the surfaces of MoS2 and CNTs. It was indicated that having a highly
dispersed CoP phase over the lamellar MoS2 phase and conductive CNT phase
brings a catalytic synergy that makes both metal phosphide and sulfide materials
as HER active phases. Furthermore, MoS2 participated in the conductive support
for CoP phase due to its strong interfacial coupling with CNTs, contributing to
(a) (NH4)2MoS4
Co(NO3)2.6H2O
100 °C, 3 h
Reflux aMoS2+x
Nickel foam CoS-doped β-Co(OH)2
(b) (c) (d)
(e) (f) 0.00

0
1.0 M KOH
–0.02 10 mA cm–2
1 mA cm–2
–0.04
–5 –0.06
–0.08
–0.10
–10
–0.07 V Glassy carbon –0.12
aMoS3 –0.14
–15 Nis–Ni(OH)2/aMoS2+x
–0.16
CoS–Co(OH)2/aMoS2+x
–0.18
20% Pt/C
–20 –0.20
–0.4 –0.3 –0.2 –0.1 0.0 0.1 0.2 0.3 0 20 000 40 000 60 000 80 000 100 000
Potential (V vs. RHE) Time (s)
(g) 20 (h)
Glassy carbon 1.64 10 mA cm–2
aMoS3 1 mA cm–2
1.62
15 Nis–Ni(OH)2/aMoS2+x
CoS–Co(OH)2/aMoS2+x
IrO2
1.60
10 1.58
–0.06 V
1.56
5
1.54
0 1.52
1.50
1.2 1.3 1.4 1.5 1.6 1.7 0 20 000 40 000 60 000 80 000 100 000
Potential (V vs. RHE) Time (s)
Figure 2.7 (a) Schematic illustration of the fabrication process of

CoS@Co(OH)2 @aMoS2+x @NF and the corresponding (b) low and high (inset: scale bar,
500 nm) SEM image. (c) TEM images with the constituting CoS (green square), Co(OH)2
(blue square), and aMoS2+x (yellow square: scale bar, 10 nm) phases. (d) HRTEM image of
β-Co(OH)2 phase in the blue square in (c). The inset of d shows the corresponding fast
Fourier transform (FFT) image. (e) HER polarization curves of aMoS3 ,
NiS@Ni(OH)2 @aMoS2+x , CoS@Co(OH)2 @aMoS2+x , and commercial 20 wt% Pt/C catalysts
in 1 M KOH. (f) Cathodic chronopotentiometric responses of CoS@Co(OH)2 @aMoS2+x at
current densities of 1 and 10 mA cm−2 . (g) OER polarization curves of aMoS3 ,
NiS@Ni(OH)2 @aMoS2+x , CoS@Co(OH)2 @aMoS2+x , and commercial IrO2 catalysts in 1 M
KOH. (h) Anodic chronopotentiometric responses of CoS@Co(OH)2 @aMoS2+x at current
densities of 1 and 10 mA cm−2 . Source: Reproduced from Yoon and Kim [36]. Copyright
2016, Wiley.
the enhanced exposure of CoP active site at the catalyst–electrolyte interface. The
electron conductivity and specific surface area provided by CNTs substantially
helped the overall performance. Moreover, in CoP phase, an improved charge
transfer from Co to P atoms was observed owing to the charge separation between
these species that ultimately gave a covalent characteristic to Co—P bond with
a hydrogenase enzyme-mimicking effect in CoP phase. Considering the features
emerged by heterostructuring metallic non-oxide and nanocarbon phases, the
developed CoP@MoS2 @CNTs hybrid system revealed an almost zero onset over-
potential for HER, a very low overpotential of 12 mV at −10 mA cm−2 , and a small
Tafel slope of 42 mV dec−1 in acidic media.
2.1.7.3 Mixed Metal Oxide/Metallic Non-oxide Multicomponent

Heterostructures
Another active hybrid catalyst rapidly developed for water splitting reactions during
the recent years is multicomponent system based on heterointerfacing TMOs and
non-oxides. Such mixed-phase heterostructures improve the electrocatalytic reac-
tion by the innate properties of oxygen- and heteroatom-involving metallic struc-
tures, and the interfaces emerged between them [45]. For example, a multicom-
ponent catalyst was developed from Co and Mo bimetallic phases and their active
metal hydroxide and chalcogenide structures for overall water splitting electrocatal-
ysis [36]. A 3D CoS-doped β-Co(OH)2 @amorphous MoS2+x heterostructure was pre-
pared by a hydrothermal process in which the MoS2+x phase was amorphous with
unsaturated sulfur sites for HER. Also, at the same time, β-Co(OH)2 phase pro-
vided the active sites for OER. CoS also served as a bridging phase to connect the
hydroxide and sulfide phases with electron/ion transfer channels between them, all
contributing to the emerged interphasic catalytic synergy for a bifunctional activity.
As a result, the reported CoS@β-Co(OH)2 @MoS2+x multicomponent catalyst exhib-
ited a powerful alkaline water splitting performance, delivering 10 mA cm−2 with an
overpotential of 350 mV and also a durable performance at 1.6–1.8 V (vs. RHE) for
more than 100 000 seconds (Figure 2.7).
2.2 Heterostructures for Electrochemical CO2

Reduction Reaction
Beside the water-energy cycle, carbon-energy cycle is also broad pathway for
heterogeneous electrocatalytic energy conversion, which has attracted many
attentions during the past decade, especially regarding the adverse impacts of fossil
fuel-based technologies including the global climate change [46]. Carbon dioxide
(CO2 )-generating technologies have escalated CO2 emission in the atmosphere
contributing to life-changing catastrophes in the new millennium. Electrochemical
CO2 reduction reaction (CRR) to value-added chemicals not only is a potential
scheme for solving this issue but also pave the way of the transformation to
sustainable and green economy along with the developed “hydrogen economy”
from the water-energy cycle with electrochemical water splitting technology. The
adsorption, bonding, and transformation of CO2 molecules over heterogeneous

catalysts are highly structure dependent, provoking structure–activity relationships
for CO2 intermediates and leading to the varied energy output requirements for a
wide range of hydrocarbon products [47].
Electrochemical CRR is highly sluggish and complex and demands highly efficient
electrocatalysts for rapid activation and adsorption of CO2 molecules over surface
active sites, with low overpotentials and high stability and selectivity toward differ-
ent CRR products. During the past decade, studies were conducted for CRR catego-
rizing the active materials as catalysts based on composition, structure, and surface
chemistry [48]. In this section, the most promising researches and recent develop-
ments on nano-heterostructured materials for CRR are described in Table 2.3.
2.2.1 Metal/Metal Oxide-Based Heterostructures

Forming heterojunctions and nanointerfaces between two metal-based electrocata-
lysts has been established as a promising strategy to boost the electron transfer and
intrinsic activity of the CRR-active transition metal compounds. Electron transfer
is strengthened at the junction of two metals or a metal and a metal oxide which is
an effective way of tuning the electronic structure of the final hybrid material and
reducing the binding energies of CO2 adsorption, key intermediates, surface associ-
ation, and subsequent electrocatalytic conversion and dissociation into the desired
products [64]. Developing metallic phase–metal oxide heterointerfaces is a common
strategy to design state-of-the-art CRR catalysts. For example, Li et al. [65] prepared
a Cu-based heterogeneous catalyst with an interface between metallic Cu phase and
Cu2 O for the efficient electroreduction of CO2 to formate. Hu et al. [49] synthesized
an oxygen vacancy-rich Sn@SnO2 interface in partially reduced Sn@SnO2 porous
hollow fibers for the selective formate production. Cai et al. [66] described a coop-
eration strategy by fabricating an effective metal–metal oxide interface between Ag
and SnOx for the potential-dependent conversion of CO2 to CO and formate prod-
ucts. Wang et al. [50] investigated In@TiO2 nanocomposite structures to efficiently
stabilize CO2 − intermediates to obtain formate with high Faradaic efficiency (FE).
Varandili et al. [67] stabilized interfacial active sites in Cu@CeO2−x nanocrystalline
heterodimers with highly mismatched metallic and metal oxide domains to improve
CO2 reduction to methane. Li et al. [51] designed a core–shell Cu@SnO2 heterostruc-
ture with a Sn-thickness-dependent CRR activity for the highly selective generation
of CO and formate.
Recently, Ren et al. reported atomic layer deposition of ZnO on CuO as a
core–shell heterostructure and the corresponding dynamic structural evolution
through in situ electroreduction to a Cu@Zn bimetallic catalyst [68]. The authors
demonstrated that such in situ transformation into metallic dual-phase heterostruc-
ture facilitates the selective CRR toward ethanol production. It was discussed that
Zn atoms migrate to the interface of Cu—Zn bimetallic phases and blend with
Cu atoms. The in situ derived Cu@Zn catalyst revealed preferred activity toward
ethanol product with a selectivity ratio of five times for ethanol-to-ethylene product
ratio at any applied potential. An FE of 41% for C2+ liquids was achieved using this
Table 2.3 Recent advances in nonprecious metal-based nano-heterostructured electrocatalysts for

electrochemical carbon dioxide reduction reaction (CRR).
Experimental Reference
Heterointerfaces Electrocatalyst Application conditions Results no.
Metal/metal Sn@SnO2 CRR Electrode: GCE FEHCOO− : a) 82.1% [49]

oxide Electrolyte: (at −1.6 V)b)
KHCO3 0.1 M b: 68 mV dec−1
Scan rate: 10 S: 10 h (at −1.6 V)
In@TiO2 Electrode: Ti FEHCOOH : 86% [50]
sheet (at −1.6 V)b)
Electrolyte: KCl b: 84 mV dec−1
0.1 M S: 24 h (at −1.6 V)
Scan rate: 50
Cu@SnO2 Electrode: CFPc) FECO : 93% [51]
Electrolyte: (at −0.7 V)
KHCO3 0.5 M
Scan rate: 5
Metal oxide Zn2 SnO4 @SnO2 CRR Electrode: GCE FEHCOOH : 77% [52]
KHCO3 0.1 M S: 24 h
(at −1.08 V)
Bi2 O3 @CuO Electrode: GCE FEHCOO− : 89.3% [53]
Electrolyte: (at −1.4 V)b)
Scan rate: 100 S: 10 h (at −1.4 V)
SnO2 @CuO Electrode: FEHCOO− : 74.1% [54]
GD-CFPd) (at −1.0 V)
Electrolyte: S: 30 h (at −1.0 V)
KHCO3 0.5 M
Scan rate: 5
Metal/ CuCo@NC CRR Electrode: Ti foil FECH3 OH : 60.2% [55]
heteroatom- Electrolyte: (at −2 V)
doped porous H2 SO4 + NaHCO3 S: 7 h (at −2 V)
carbon 0.5 M
Sn@NC Electrode: CFP FEHCOO− : 65% [56]
Electrolyte: (at 690 mV)e)
KHCO3 0.1 M FECO : 91%
(at 490 mV)f)
b: 79 mV dec−1
SHCOO− : 24 h
(at −0.8 V)
SCO : 24 h
(at −0.6 V)
NiSA–N–CNT Electrode: CFP FECO : 91.3% [57]
KHCO3 0.5 M S: 12 h (at −0.7 V)
Metal SnO2 @N– CRR Electrode: GCE FEHCOO− :: 46% [58]

oxide/porous MWCNTs Electrolyte: (at −0.9 V)f)
carbon based KHCO3 0.1 M S: 10 h (at −0.9 V)
CuO@Nx C Electrode: CFP FEC2 H4 : 36% [59]
NaHCO3 0.1 M
SnO2 @C Electrode: CFP FECO : 21.8% [60]
KHCO3 0.1 M FEHCOO− : 54.2%
Scan rate: 5 (at −0.9 V)
bCO : 127 mV dec−1
bHCOO− : 187 mV
dec−1
S: 12 h (at −0.9 V)
Metal Ni3 N@ CRR Electrode: GCE FECO : 89% [61]
non-oxide MWCNTs Electrolyte: (at −0.53 V)
NaHCO3 0.5 M b: 182 mV dec−1
Scan rate: 50
Fex N@Fe–N–C Electrode: GCE FECO : 95% [62]
S: 24 h (at −0.53 V)
MoP@In-PC Electrode: CFP FEHCOOH : 96.5% [63]
Electrolyte: (at −2.2 V)6
[Bmim]PF6 / b: 112.6 mV dec−1
MeCN/H2 O S: 24 h (at −2.2 V)f)
Scan rate: 20
a) Faradaic efficiency.
b) Potential against saturated calomel electrode (SCE).
c) Carbon fiber paper.
d) Gas diffusion carbon fiber paper.
e) Faradaic efficiencies recorded at the corresponding overpotential values.
f) Potential against Ag/AgCl electrode.
bimetallic heterostructure, which was even furthered to 48.6% with a −97 mA cm−2
partial current density at a low potential of −0.68 V vs. RHE in 1 M KOH upon
changing the electrochemical H-cell to a flow cell. It was also found out that carbon
monoxide (CO) binding on Cu active sites was promoted by interfacing the Zn
phase. Hence, free CO and adsorbed *CH3 intermediates were shown to combine,
forming *COCH3 intermediate, which was ultimately transformed into ethanol
with high selectivity.
2.2.2 Metal Oxide-Based Heterostructures

The formation of nano-heterointerfaces between active oxide phases of CRR-active
metals is one of the most promising strategies to reduce the large energy barriers
for the electrochemical activation and the subsequent conversion of CO2 molecules
in aqueous media. It has been reported that the transport of electrons from het-
erostructured catalysts to the surface-absorbed CO2 molecules and *COO⋅− as the
key intermediate is facilitated compared with the pure/single-phase TMOs, due to
the augmented intrinsic electronic structure at the interface of two or more TMO
structures [69]. For example, Wang et al. [52] elucidated the band alignment in
Zn2 SnO4 @SnO2 heterostructure affording efficient CRR. Dai et al. [53] reported
controllable formation of Bi2 O3 @CuO heterostructure for highly selective electrode
reduction of CO2 to formate product. Fan et al. [54] operated aqueous-phase CRR
on SnO2 @CuO nanocomposite catalyst for the selective formate formation. Li et al.
[70] reported highly selective CRR to CO through interface tuning at CuO@Sb2 O3
nanocomposite. Albo et al. [71] successfully produced methanol as the main
product of CRR over Cu2 O@ZnO heterostructure.
Recently, Wang et al. performed phase and structure engineering on copper–tin
nanoparticles to form oxide heterostructures with optimized CRR activity [72].
It was shown that such phase/structure modulation of transition metal-based
catalysts can effectively regulate the electrocatalytic performance. Three distinct
Cu@SnO2 heterostructured catalysts with different metallic phases and structures
were prepared through a facile post-thermal annealing treatment of bimetallic
CuSn nanoparticles at controlled temperature and atmosphere conditions, namely,
CuO@hollow SnO2 structure (at 250 ∘ C for one hour in air), Cu41 Sn11 core–shell
structure (at 250 ∘ C for one hour in H2 /N2 5 : 95 v:v), and Cu nanoparticles@hollow
SnO2 Janus structure that was formed by further annealing the CuO@hollow SnO2
structure in H2 /N2 5 : 95 v:v at 250 ∘ C for another one hour. The first batch of
the engineered heterostructures with CuO and hollow SnO2 phases exhibited the
best CRR activity with boosted CO partial current densities at −0.7 V vs. RHE, 5.9
and 5.3 times higher than those of other two heterostructures, and significantly
improved formic acid (HCOOH) partial current densities at −1.0 V vs. RHE,
33.2 and 3.4 times higher than those of single-phase Cu nanoparticles and SnO2
nanoshells on carbon support, respectively. The observed optimal performance
of CuO@hollow SnO2 heterostructure was achieved by tuning the range of CRR
products from carbon monoxide CO to HCOOH at high FE through varying the
applied bias potential from −0.7 to −1.0 V vs. RHE, approving the investigated
correlation between the phase/structure and catalytic activity. The obtained promis-
ing performance was assigned to the abundant and strong CuO–SnO2 interfaces
that effectively reduced the reaction free energies attaining *COOH intermediate
species. Long-term performance of at least 10 hours was achieved with negligible
loss in activity and selectivity for the phase/structurally engineered Cu@SnO2
heterostructures.
2.2.3 Metal/Heteroatom-Doped Porous Carbon-Based

Heterostructures
Heteroatom-doped porous carbon is a potential active phase for constructing
metal-based nano-heterostructures. Advantages such as low cost, facile prepa-
ration, good electrical conductivity, tunable surface chemistry, inherent activity
for CO2 adsorption, and sluggish kinetics toward HER (in aqueous solutions)
make it an ideal nonmetallic framework for CRR [73]. Such porous carbonaceous
frameworks have great potential to obviate the existing issues for the low efficiency
in CRR process, i.e. insufficient electron transfer and high binding energy of CO2
intermediates [74]. Particularly, when hybridized with metal phase, the insertion of
a metal/heteroatom/carbon interface with abundant metal–heteroatom sites would
effectively boost the exposed atomic interface and allow for the improved electron
transfer capacity [75]. One common issue in the heterostructures of metal–carbon
interface is the low metal loading content that reduces the distance between
metal–heteroatom–carbon interfaces, and the electron flow over the surface,
hence greatly contributes to the limited reduction of CO2 -adsorbed intermediates
[55]. Interface modulation and tuning metal size and morphology have been
suggested as effective strategies to tackle these issues. For example, Cheng et al. [55]
depicted efficient reduction of CO2 to over atomically dispersed dual CuCo sites on
nitrogen-doped carbon (CuCo@NC). Büchele et al. [76] elucidated the impact of
structural sensitivity and Ni single atom-phase evolution in nitrogen-doped carbon
frameworks on the highly efficient CRR to CO.
Also, Zhao et al. reported tunable interface between Sn metal and nitrogen-doped
porous carbon nanofibers for a switchable CRR in aqueous solutions [56]. Sn@NC
nanofiber composites were prepared by a two-step electrospinning–pyrolysis pro-
cedure. Sn nanoparticles anchored on nitrogen-doped carbon nanofibers facilitated
the formation of formate product with a high current density of 11 mA cm−1 and an
FE of 62% at a moderate overpotential of 690 mV. By tuning Sn phase to atomically
dispersed Sn on NC phase, a highly efficient CRR to CO product was attained with
an FE of 91% at a low overpotential of 490 mV. It was demonstrated that the interfa-
cial electronic interaction between Sn and pyridinic nitrogen atoms upon different
Sn distribution influenced the tuning of activity and selectivity.
Cheng et al. made single-atom heterostructured catalysts based on various atomi-
cally dispersed transition metals on CNTs with ultrahigh metal loading for a selective
structure–activity relationship [57]. Benefiting from an ultrafine size, high atomic
efficiency, activity, and selectivity were achieved for atomically dispersed Ni and Co
metals and dual-metal site NiCo and CoFe phases on nitrogen-doped CNTs with an
ultrahigh content, 20 wt% for Ni single atoms, using a multistep pyrolysis procedure.
Ni single atom-based catalyst (NiSA–N–CNT) was the most active material for CRR
to CO formation, giving a high TOF of 11.7 s−1 for CO2 -to-CO conversion at −0.55 V
vs. RHE, which was about 2 orders of magnitude higher than the activity recorded
by Ni nanoparticles on CNTs (Figure 2.8).
(a) (b)
200 nm 2 nm
(c) (d)
0.33 Å
2 nm 1 nm
(e) 0 (f) 0
0
–10 –1
j (mA cm–2)
j (mA cm–2)
–2 –5
–20 –3 Ni–N–CNT–N2
–4 Ni–N–CNT–CO2
–0.5 –0.4 –0.3 –0.2 –10
–30 NiSA–N–CNT–N2 Ni–CNT–N2
NiSA–N–CNT–CO2 Ni–CNT–CO2
–40 –15
–0.8 –0.6 –0.4 –0.2 0.0 –0.8 –0.6 –0.4 –0.2 0.0
(g) E (V vs. RHE) E (V vs. RHE)
(h) 100
Yield (10–3 mM cm–2 min–1)
5.0 NiSA–N–CNT
CO Ni–N–CNT
4.0 80 N–CNT
H2 Ni–CNT
3.0 60
FE (%)
2.0
40
1.0
20
0.0
N
N
iS
0
N
i–
A–
–0.6 –0.4 –0.2

–C
N
N
0.0
N
–C
i–
–C
C
E (V vs. RHE)
T
N
N
N
T
T
T
Figure 2.8 (a, b) SEM and aberration-corrected scanning transmission electron

microscopy-annular dark-field (AC-STEM-ADF) images of NiSA-N-CNTs. (c) Annular
dark-field (ADF) image of Ni single atoms located on the walls of a CNT (red circles show Ni
atoms embedded in the carbon plane of walls. The inset is FFT image of (c)). (d) ADF image
of the structure environment of Ni single atoms. CRR LSV curves of (e) NiSA-N-CNTs and
(f) Ni-N-CNTs heterostructures in 0.5 m N2 - and CO2 -saturated KHCO3 solution. (g) Product
yields of NiSA-N-CNTs, Ni-N-CNTs, N-CNTs, and Ni-CNTs catalysts for CRR at −0.55 V. (h) CO
FE of NiSA-N-CNTs, Ni-N-CNTs, N-CNTs, and Ni-CNTs catalysts at −0.28, −0.40, −0.55, and
−0.70 V. Source: Reproduced from Cheng et al. [57]. Copyright 2018, Wiley.
2.2.4 Metal Oxide/Porous Carbon-Based Heterostructures

The main driving force for the fabrication of TMO–(nano)carbon heterointerfaces is
boosting the poor electron conductivity of metal oxides by a porous carbonaceous
phase with large surface area. Besides carbon materials such as graphene, CNTs
and heteroatom-doped porous carbon (i.e. nitrogen, sulfur, phosphorous, etc.) are
the most common carbonaceous frameworks for nano-heterostructures in electro-
catalysis. Particularly, chemically modified porous carbon with induced defect sites
and improved surface basicity can be considered as nonmetal active phase for CRR.
For instance, Zhang et al. [58] measured facilitated formation of formate from CO2
in aqueous KHCO3 solutions using a hybrid of nitrogen-doped multiwalled CNTs
decorated with SnO2 nanoparticles (SnO2 @N–MWCNTs). Yang et al. [59] showed
improved selectivity for ethylene on N-doped carbon-supported CuO (CuO@Nx C)
hybrid heterogeneous CRR catalyst. Ning et al. [77] depicted the efficiency of cubic
Cu2 O phase when confined in nitrogen-doped carbon shells (Cu2 O@NCS) for fea-
sible ethylene generation from CO2 .
Yiliguma et al. [60] used sub-5 nm SnO2 nanoparticles chemically coupled with
hollow carbon spheres (SnO2 @C) as an efficient formate-selective CRR heterostruc-
ture. Both activity and stability of the hybrid catalyst relied on micro/nanostructure
of SnO2 phase that revealed superiority over plain SnOx nanoparticles agglom-
erated in hollow carbon spheres. The developed hybrid afforded high electronic
conductivity and surface-to-volume ratio to improve charge and mass transport
processes during the CRR. The hybridization brought Sn–O–C structural linkages
between SnO2 ultrafine nanoparticles and carbon microspheres that augmented
the CO2 chemisorption, the electron transfer rate between these two phases, and
the number of Sn-based catalytically active sites. The evolved interfacial Sn–O–C
linkages modulated the electronic structure of Sn4+ species, leading to the boosted
intrinsic activity, and were highly effective for the catalyst durability. Benefiting
from these advantages, SnO2 @C heterostructure showed a formate FE of 54.2%
at −0.9 V vs. RHE with good electrochemical stability for over 12 hours in 0.1 M
KHCO3 electrolyte.
2.2.5 Metal Non-oxide-Based Heterostructures

Transition metal non-oxides have emerged as potential candidates for efficient
CRR, especially when hybridized with (hetero-doped) (nano)carbon materials. One
interesting entity in transition metal non-oxide-based heterostructures is the in

situ-formed metal–heteroatom–carbon interfaces repeatedly reported during the
recent years as alternative modulating sites for molecular and intermediate CO2
adsorption and reduction. Moreover, metallic non-oxides have been incorporated
to (nano)carbon with promoted electronic synergy and charge transfer between
metal and carbon phases. For instance, Wang et al. [61] demonstrated the use of
nickel nitride incorporated on multiwalled carbon nanotubes (Ni3 N@MWCNTs)
for selective acidic electroreduction of CO2 to CO.
Cheng et al. encapsulated iron nitride in iron–nitrogen–carbon interfaces that
resulted in a strong CRR for CO formation [62]. The proposed synthesis design
involved consecutive electrospinning, carbonization, acid leaching, and nitridation
(under ammonia atmosphere) steps enabling the confinement of Fex N nanoparti-
cles within Fe- and N-co-doped carbon layers to obtain a core–shell Fex N@Fe–N–C
heterostructure. A CO2 -to-CO conversion selectivity near unity was resulted with
Fex N@Fe–N–C hybrid catalyst having an FE of about 95%, a current density of
4.71 mA cm−2 , and an excellent durability for 24 h at −0.53 V vs. RHE. Supported by
theoretical calculation, the designed non-oxide heterostructure revealed a promoted
CO-related intermediate adsorption on Fex N core from the Fe/N-co-doped shell,
while Fe–N4 –C shell became deactivated readily upon CO generation. It was
proposed that the encapsulation of Fex N moieties into the core–shell composite
substantially decreased the CO bonding strength, making Fe a strong active site
for CRR.
Sun et al. reported In-doped porous carbon-supported molybdenum phosphide
nanoparticles (MoP@In-PC) as a highly selective CRR electrocatalyst for the forma-
tion of formic acid [63]. An In metal–organic framework (In-MOF, MIL-68), syn-
thesized by solvothermal method, was used as the precursor of In-doped porous
carbon phase. MoP nanoparticles as catalytic sites provided a strong CO2 adsorption
and electrolyte diffusion to the electrode surface. This porous carbon effectively con-
trolled the size of MoP nanoparticles for a prolonged CRR stability. Furthermore, the
metal-doped support supplied additional In2 O3 species on the extended specific sur-
face of carbon, facilitating a stronger adsorption of CO2 ⋅− intermediate. As a result,
a high FE of 96.5% and a current density of 43.8 mA cm−2 were obtained for CO2
electroreduction to formic acid in acetonitrile/water (5 wt%) aqueous solution with
1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim][PF6 ], 30%) as the sup-
porting electrolyte (Figure 2.9).
2.2.6 Multicomponent Metal-Based Heterostructures

The majority of the developed CRR electrocatalysts were designed as single-
component materials or two-component composites based on CRR scaling and
structure–activity relationships [48b, e]. Recently, multicomponent heterostructures
have emerged as highly efficient CO2 -converting catalysts. A main phase in most of
these heterostructures is (nano)carbon materials owing to their good electronic con-
ductivity. In addition, most of the carbon phases are porous, allowing for expanded
electrochemically active surface area and electronic coupling with active metallic
(a) (b)
(c) (d) 100

120 MoP@In-PC
Faradaic efficiency (%)

MoP@Ga-PC 80 a
100
MoP@PC-1
MoP@PC-2 b
80 60
Bulk MoP
60 c
40
40 d
20 20
e
0
0
–0.8 –1.2 –1.6 –2.0 –2.4 –1.9 –2.0 –2.1 –2.2 –2.3 –2.4
(e) Potential (V vs. Ag/Ag*) (f) Potential (V vs. Ag/Ag*)
50 0.28
e: 170.8 mV dec–1
40 a 0.24 b: 126.0 mV dec–1

c: 142.8 mV dec–1
0.20
30 b
0.16
η(V)
c
20 0.12
d
10 0.08
e d: 145.9 mV dec–1
0.04 a: 112.6 mV dec–1
0
0 1 2 3 4 5 6 –1.2 –0.8 –0.4 0.0 0.4 0.8 1.2
Time (h) log (∣ jformate∣ (mA cm−2))
Figure 2.9 (A) TEM and (B) HRTEM images of MoP@In-PC hybrid with characterized
crystal lattice of MoP. CRR in CO2 -saturated [Bmim]PF6 (30 wt%)/MeCN/H2 O (5 wt%)
electrolyte. (C) The LSV curves and (D) Faradaic efficiency for formic acid catalyzed by
MoP@In-PC (a), MoP@Ga-PC (b), MoP@PC-1 (c), MoP@PC-2 (d), and bulk MoP (e) at the
applied potentials for 6 h. (E) Current–time curves of the five catalysts at −2.2 V
(vs. Ag/Ag+ ). (F) Tafel plots for formic acid production catalyzed by above catalysts. Source:
Reproduced from Sun et al. [63]. Copyright 2018, Wiley.
phases [48d, 69]. Still, the efforts to develop CRR catalysts with catalytic/electronic
synergy and ensemble effects between the different active phases are limited, and
currently the complex CRR systems heavily rely on metallic oxide heterostructures.
In this section, we presented the recent multicomponent metallic oxide-based
heterostructures for CRR, as shown in Table 2.4.
Table 2.4 Recent advances in nonprecious metal-based multicomponent nano-heterostructured

electrocatalysts for electrochemical carbon dioxide reduction reaction (CRR).
Metal Cu2 O@CuO@Ni CRR Electrode: CFa) FECO : 95% [78]

oxide/metal Electrolyte: (at −1.2 V)
oxide/metal KHCO3 0.5 M b: 114 mV dec−1
Scan rate: 20 S: 25 h (at −1.2 V)
CuO@Cu2 O@Cu Electrode: CF FEC2 H5 OH : 31% [79]
KHCO3 0.1 M FECH3 OH : 14%
(at −0.3 V)
FEHCOO− : 6%
(at −0.3 V)
b: 213 mV dec−1
S: 18 h (E:
−0.3 V)
Metal oxide/ Cu@SnOx @CNT CRR Electrode: CFP FECO : 89% [80]
metal/nonmetal Electrolyte: (at −0.99 V)
KHCO3 0.1 M FEHCOOH : 77%
(at −0.99 V)
Metal CuO@Sb2 O3 @C CRR Electrode: CFP FECO : 90% [70]
oxide/nonmetal KHCO3 0.1 M b: 121.2 mV dec−1
Scan rate: 5 S: 10 h (at −0.8 V)
Metal Cu2 O@CuO@CuS CRR Electrode: CMb) FEHCOO− : 84% [81b]
oxide/metal KHCO3 0.1 M S: 8000 s
non-oxide (at −0.7 V)
Scan rate: 10
a) Cupper foam.
b) Cu mesh.
2.2.6.1 Metal Oxide-Based Multicomponent Heterostructures

2.2.6.1.1 Transition Metal Oxide/Metal Oxide/Metal Heterointerfaces
The most intriguing feature in CRR catalysts is their high selectivity toward the
activated CO2 intermediates and the related hydrocarbon products. Copper has
a unique position among CRR-active metals, and the related structures often
have promising activity for binding to CO* intermediates, converting CO* to
COH* or CHO* intermediates, and finally for alcohol and hydrocarbon production
[48d, 82]. Among them, Cu2 O is vastly investigated particularly for C2 H4 generation;
however it often suffers from poor selectivity and stability [77]. For this reason,
multicomponent Cu2 O heterostructures have been studied to improve these issues.
The applied strategies involve surface and interface engineering to modulate the
intrinsic activity of individual catalytic centers and surface charge distribution and
Another random document with
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Au lieu d’élever la France, en faisant de cette patrie des hommes, la
patrie des hommes et des femmes, en centuplant par la coopération de
tous ses habitants, la puissance d’irradiation du pays, flambeau de
l’humanité; ceux qui se qualifient patriotes, souffrent que la France soit
rapetissée par l’annulement de plus de la moitié de ses enfants. Ils
tolèrent que la patrie soit dépouillée du concours moral et intellectuel des
vingt millions de femmes. La France amputée des femmes, n’est qu’une
demi-France, tandis que la France où les femmes voteraient et
légiféreraient conjointement avec les hommes, serait une France et
demie.
Quand augmentera-t-on notre patrie, en cessant d’en faire un clan
restreint au sexe masculin de l’univers?
XIV
Sentiments et systèmes. L’âge et le sexe
Les féministes victorieuses des autres pays, qui ont mis ou qui veulent
mettre la main au gouvernail, font des sentiments et des systèmes, une
question secondaire. En France au contraire, des revendicatrices prônent
leur conception personnelle de l’amour et de la politique. Cette manière
d’agir qui divise les femmes, retarde chez nous le triomphe du féminisme.
Les Françaises seraient bien plus libres qu’elles ne sont, si elles
n’avaient pas pour but unique dans la vie l’éphémère amour! Elles
s’épargneraient souvent d’être dupes de l’homme, si, avant que de lui
faire le don d’elles-mêmes, elles s’efforçaient de le connaître.
Malheureusement bien des femmes qui ne prêteraient pas vingt francs
sans savoir si leur emprunteur est probe, se donnent tout entières avant
de s’informer de ce que vaut la moralité de leur amoureux.
Il serait puéril d’exiger que les hommes accomplissent des devoirs
dont la loi les dispense. Selon qu’elle est bien ou mal faite, la loi moralise
on démoralise l’individu.
Ne vous attendez pas à voir régner la vraie république dans l’Etat tant
que la monarchie subsistera légale au foyer.
Les articles du code qui incitent l’homme à mépriser sa mère, l’époux à
mépriser sa compagne, le sexe masculin à mépriser le sexe féminin,
pervertissent le sens moral de la nation et font qu’aimer et être bon n’est
pas la vraie recette pour être heureux. C’est au contraire la recette
infaillible pour bien souffrir. Quiconque a une âme noble, un cœur d’élite
est tout le long de la vie meurtri. On s’imagine que la force attractive qui
pousse les êtres les uns vers les autres, est la garantie du bonheur
conjugal.
L’amour rend les humains seulement plus aptes à commettre des
erreurs, puisqu’en leur enlevant toute lucidité il les empêche de discerner
s’il y a entre eux l’antipathie qui les fera ennemis, ou la concordance de
goûts, de pensées, de sentiments d’où résultera leur union morale, la
fusion de leur moi.
Combien peu d’êtres sont capables de se comprendre... Ils existent
peut-être mais inconnus les uns aux autres. Si ceux qui ont une âme
identique se trouvaient face à face, ils ne s’aimeraient pas, car chacun est
séduit par le contraste. L’homme grave, le savant sera attiré par
l’insouciance d’une enfant. La femme sérieuse, instruite, aimera n’importe
quel fou. C’est cette loi éternelle qui cause les déchirements de ceux qui
aiment.
Et les hommes trahis trouvent l’apaisement de leurs tourments. Ils ont
tous les moyens pour oublier leur peine. Le meilleur est la politique qui
leur permet de transporter leur activité cérébrale et affective du «home»
solitaire, en la commune et l’Etat où tant d’intérêts passionnants se
disputent leur sollicitude.
Aux deux sexes souffrant de l’inconstance, il serait rationnel d’offrir les
mêmes remèdes. Pourquoi le moyen de rattacher à l’existence, en se
préoccupant d’organiser une vie meilleure aux générations, ne serait-il
pas donné aux femmes comme aux hommes désespérés?
Les femmes soumises comme les hommes aux règles légales et aux
charges sociales, n’ont pas seulement le droit indéniable de participer à la
politique, elles ont besoin d’y participer afin de trouver là un point d’appui,
quand, par le fait de la mort ou de l’abandon de leur compagnon, le sol
manque sous leurs pieds.
Les hommes, pris par mille occupations diverses, n’apportent pas une
attention suffisante à l’amélioration des conditions d’existence des
masses, mais les femmes sans rôle ni but, les veuves, les abandonnées,
concentrant là leurs énergies accumulées, pourraient aider à résoudre des
problèmes qui aujourd’hui semblent insolubles, parce que concernant
l’humanité tout entière, les seuls efforts masculins sont impuissants à en
donner la clef.
Plutôt que de laisser le chagrin miner la vigueur, et l’obsession des
regrets troubler les cerveaux, ne vaudrait-il pas mieux faire sortir, de
l’excès des tortures individuelles, la rédemption générale?
L’âge et le sexe
La différence d’âge des époux rend souvent aussi impossible le
bonheur conjugal. Généralement le mari est beaucoup plus âgé que la
femme. Cependant la grande Mademoiselle Louise d’Orléans duchesse
de Montpensier, avait six ans de plus que Lauzun. Talma, avait 28 ans
quand il se maria et sa femme, Julie Carreau, 37 ans.
Ce sont là des exceptions: d’ordinaire l’époux a de 8 à 12 ans de plus
que l’épouse, parce que soit-disant, la femme vieillit plus vite que
l’homme.
Le préjugé relatif à l’âge de la femme n’est qu’un moyen de
domination. L’homme bedonnant et blanchissant peut, s’il le veut, être
amoureux; son cœur à lui ne vieillit pas, tandis que si une femme qui n’est
plus jeune laisse deviner son besoin d’aimer, elle paraît ridicule.
Le sexe masculin s’est concédé la jeunesse éternelle, peut-être à tort,
car son organisme n’est point aussi résistant que celui du sexe féminin.
Si nous en croyons les statistiques, le sexe-minorité a beaucoup moins
de vitalité que le sexe-majorité, puisque trente mille hommes de plus que
de femmes meurent chaque année.
Pourquoi l’homme pourvu de moins de force vitale que la femme est-il
censé paraître plus jeune qu’elle?—Parce qu’il existe intégralement et que
la femme n’existe qu’à moitié, étant annulée en politique.
La politique tient tellement dans sa dépendance la vie sociale et
économique, que chacun, selon que son sexe y participe ou non, est
estimé en tant qu’être humain ou en tant qu’animal. Ainsi l’homme qui
vote, légifère, est apprécié au triple point de vue moral, intellectuel et
physique, tandis que la femme qui ne vote pas, l’est seulement en raison
de sa valeur physique.
La femme qui ne vote pas ne vaut que pour le service, le décor et la
reproduction. Si volontairement ou non elle s’est soustraite à son rôle
animal, on la cloue au pilori avec cette épithète «vieille fille» en laquelle
sont résumés l’égoïsme et l’acariâtreté.
C’est d’une victime du désordre social dont on a fait ce hideux hibou.
Regardez la vieille fille, cette cible vivante sur laquelle s’exerce la
méchanceté humaine, et vous serez attendri par son abnégation, son
sourire navré.
N’est pas qualifiée de vieille fille toute femme qui vieillit dans le célibat.
Une cocotte surannée, une religieuse blanchie sous la cornette, ne sont
point appelées vieilles filles.
Pour n’être pas vieille fille, il suffit de sacrifier au Dieu qui règne dans
le ciel ou au Dieu mâle qui règne sur la terre.
A quel âge la jeune fille s’entend-elle qualifier de vieille?—Dès qu’elle
sort de l’adolescence. Si, à vingt-quatre ans, elle n’est pas mariée, elle
coiffe Sainte-Catherine et entre en la confrérie des vieilles filles.
Alors même qu’en la vieillesse l’homme ne cesse d’être le jeune
premier, se croyant apte à plaire et à exciter l’amour, la fillette en sa
croissance est tourmentée par la crainte de laisser passer l’heure de
captiver l’homme. Le préjugé qui lui fait se faire un point d’honneur de ne
pas attendre vingt-cinq ans pour devenir épouse, force à s’accomplir avec
la précipitation du désespoir beaucoup d’unions mal assorties.
Si plus des deux tiers des femmes ne se marient pas en France—vingt
neuf à trente trois Françaises pour cent seulement arrivent à se faire
épouser—c’est évidemment parce que les hommes restent vieux garçons.
Or, jamais aux vieux garçons ne s’attache le ridicule jeté sur les vieilles
filles par les hommes, pour forcer les jouvencelles à s’éprendre d’eux.
On ne fait pas à l’homme, de l’état de vieux garçon, un reproche; au
contraire. On l’entoure, on le choie, on se le dispute, le vieux garçon; il est
partout le bienvenu ouvrant le champ à tous les espoirs.
La femme qui n’a jamais été sollicitée de contracter une union est
autant que celle qui a refusé de se consacrer à l’homme, traitée d’égoïste.
Alors que le garçon qui se dispense d’avoir une compagne et se fait aimer
de celles des autres, est, même par les maris, appelé galant homme.
Pourquoi, quand on apprécie les hommes qui restent célibataires, bien
qu’ayant toutes facilités de cesser de l’être, vilipende-t-on les femmes
dont il ne dépend pas de la volonté de sortir du célibat?...—Parce que les
hommes sont des êtres humains, des citoyens, et que les femmes sont
encore assimilées aux animaux.
Au lieu d’être déconsidérés, les vieux garçons sont honorés. Ils
occupent en France les hautes fonctions. Au Parlement, dans
l’administration, on ne voit que des célibataires! Le mariage est
obligatoire, seulement pour la femme, parce que la femme n’existe que
pour le mariage. Elle est encore, ainsi qu’écrivait Napoléon à Sainte-
Hélène, «la propriété de l’homme comme l’arbre à fruit est celle du
jardinier».
Le nombre des femmes étant supérieur à celui des hommes, tous les
Français consentiraient-ils à renoncer au célibat, que toutes les
Françaises ne pourraient avoir un époux. Au lieu donc de dépriser l’état
de célibataire, qui n’annihile aucunement les facultés intellectuelles, il
conviendrait de réagir contre le préjugé du mariage obligatoire pour la
femme, et d’utiliser au profit de la collectivité nationale les trésors du cœur
féminin laissés en disponibilité.
Les vieilles filles dont se gaudissent les hommes, sans doute par ce
qu’elles sont les seules femmes qui gardent sur eux des illusions, ont
généralement l’esprit ouvert aux larges pensées humaines. Il en est parmi
elles qui se lamentent de voir aussi mal utiliser par le sexe souverain, les
moyens d’amélioration sociale dont il dispose.
C’est parce qu’elle est annulée en politique, qu’elle n’est que par sa
beauté une valeur sociale, que la femme âgée est annihilée.
Avec la fonction de reproductrice finit le rôle de la femme, c’est-à-dire,
au moment précis où le rôle de l’homme ne fait que commencer.
L’homme vieux a la valeur de son mérite. Il il bénéficie du savoir
acquis, de l’expérience faite. Il doit à son âge souvent de hautes situations
pécuniaires et honorifiques, tandis que la femme vieille, donc plus
décorative, fût-elle épouse et mère, est isolée en la famille, congédiée par
la société.
Elle n’était là que pour l’ornement et qu’à titre de productrice d’enfants.
N’en mettant plus au monde et ayant cessé d’être belle, elle ne compte
plus, c’est une morte vivante!
Ce ne sera qu’en élargissant son existence par la conquête des
prérogatives politiques de l’homme, que la femme pourra faire apprécier,
en même temps que sa fugitive beauté physique, sa durable valeur
comme intellectuelle et cesser de seulement compter comme un animal
pour exister en être humain.
XV
La besogne ménagère
Travail domestique rétribué
Lentement, mais sûrement, le féminisme progresse. Lorsque nous

avions au congrès de Marseille[18], demandé que le travail ménager soit
rémunéré, que la mère allaitant ses enfants, que la femme cuisinant,
raccommodant, mettant tout en ordre dans la maison, puisse prétendre à
l’indépendance économique, notre proposition avait été jugée si hardie
qu’on l’avait qualifiée d’inconvenante et même d’immorale.
Pour certains membres de ce congrès, ne plus vouloir que la femme
soit corvéable c’était, paraît-il, sous prétexte d’indépendance et de dignité
féminine, inciter la femme à haïr son mari, pousser l’homme à considérer
sa compagne comme une étrangère, à la payer comme une prostituée.
Eh bien, ce qui épouvantait hier, semble aujourd’hui rationnel. Le
congrès de la ligue de l’enseignement qui s’est tenu récemment à
Amiens[19], a, en effet, sans qu’il s’éleva de protestations, adopté le vœu
ci-dessous:
«Que le travail de la femme dans la famille soit évalué et qu’on

prenne pour base de cette évaluation la rémunération qui serait
donnée à une salariée pour exécuter le même travail».
Evaluer un travail, c’est évidemment décider de le rétribuer.

La rémunération empêchera le travail du ménage de paraître abject.
Elle relèvera, aux yeux de l’homme, la femme qui l’accomplit et elle
rapprochera les époux.
En émettant ce vœu, la ligue de l’enseignement ne s’est pas
seulement, à l’exemple de son fondateur, Jean Macé, déclarée en faveur
de l’égalité des sexes, elle a orienté la femme vers le féminisme. Car en
s’affirmant partisans de l’équité envers la femme, les éducateurs ont
reconnu la nécessité d’apprendre à être juste à son égard.
Chez nous, ce qui maintient particulièrement la femme dans
l’esclavage, c’est la corvée domestique qui, en usant ses forces, en
prenant son temps, la laisse dénuée. La ménagère qui ne reçoit point
même de l’homme la somme indispensable pour le ravitaillement de la
maisonnée, en peinant beaucoup, en accomplissant des miracles
d’économie, est obligée de mendier à son mari quand elle a besoin de
quelques centimes.
Or, pendant que la malheureuse reste privée d’argent, l’homme qui lui
fait faire gratuitement sa part de besogne à la maison, dépense sans
compter au cabaret! Ne serait-il pas équitable qu’il remette à sa
compagne une part de salaire qu’elle lui a permis d’obtenir en se
déchargeant des occupations domestiques?
L’égoïsme est funeste même à l’homme qu’il favorise, et il est urgent
de cesser d’exploiter la femme; obliger, en effet, la procréatrice de se
surmener, c’est assurer la naissance d’un maximum d’enfants anormaux,
donc créer des charges sociales.
Actuellement, de nombreuses femmes, forcées pour vivre d’exercer un
métier, doivent, après le travail professionnel achevé, recommencer à se
fatiguer en accomplissant la besogne domestique. L’hypocrite loi qui leur
interdit la veillée pour exécuter l’ouvrage payé, leur laisse toute liberté de
passer la nuit à peiner gratuitement.
L’homme, en sortant du bureau, du magasin, de l’atelier, se repose et
se distrait, pendant que son esclave, en quittant son emploi, s’exténue
pour lui assurer logement, linge, vêtements propres, repas bien apprêtés.
Aider la femme à échapper à l’exploitation familiale, c’est la rendre
apte à mettre au monde des humains, qui, étant moins à redresser, plus
aisément se développeront.
Quand le travail de gestation et d’enfantement qui perpétue l’espèce
humaine, quand le travail domestique qui la conserve seront appréciés à
leur valeur, le préjugé du sexe disparaîtra.
Les femmes qui peinent presque sans interruption et, quasi sans
rétribution, ont leurs cris de souffrance étouffés en l’enceinte que leur fait
l’isolement.
Entre les femmes, nul point de contact; le terrain politique qui permet
aux hommes de se connaître, de s’unir pour défendre leurs intérêts
corporatifs comme leurs intérêts publics, leur fait à elles, défaut. Aussi, ne
sont-elles que quelques-unes de groupées dans des métiers où sont
surmenées, exploitées, des milliers et des milliers d’ouvrières.
Malgré que les socialistes, au pouvoir, ne puissent rien pour les
femmes tant qu’elles ne votent pas, combien, néanmoins, celles-ci en
s’associant, en donnant aux exploiteurs la peur d’un concert de plaintes,
pourraient améliorer leur sort!
C’est moins relativement à la limitation des heures de travail de la
femme—limiter le travail féminin qui ne s’achève là que pour reprendre
ailleurs, est une amère ironie—que, contre la condamnation de la femme
à un double labeur: l’un à peine payé, l’autre tout à fait gratuit, que devrait
se porter l’effort féministe.
Si, dans une usine ou une fabrique, la moitié des employés disait à
l’autre moitié en désignant un ouvrage rebutant: «Chargez-vous de cette
ingrate besogne qu’il ne nous plaît point de faire. Vous ne recevrez pour
cela aucune indemnité, mais nous nous ferons rétribuer le temps que
vous emploierez à accomplir à notre place, notre part de ce travail; et, si
vous avez soin de bien nous disposer envers vous, aussi longtemps que
cela nous sera agréable, sans trop nous faire tirer l’oreille, nous
subviendrons à votre entretien. Les dupeurs proposant ce marché,
seraient vite remis à leur place par ceux qu’ils voudraient exploiter.
Eh bien, la convention, qu’en aucun cas jamais des hommes ne
pourraient faire accepter par d’autres hommes, est subie par les femmes.
Beaucoup de Françaises ont dans leur ménage la position d’un enfant
auquel, dans un moment de générosité, on promet un jouet, dans
l’occurrence, un objet de toilette; la somme nécessaire à son habillement
ne lui étant donnée comme une faveur, que pour chaque objet.
Si le pivot de la famille est ainsi humilié, c’est un peu sa faute. Il
suffirait que les femmes qui s’usent au travail improductif, se missent en
grève pour que l’homme fût contraint ou de les indemniser pour les servir,
ou de distraire quelques heures de son temps rétribué, pour se servir lui-
même. Si la grève des mineurs en raréfiant le combustible peut arrêter le
machinisme, la grève des ménagères forcerait, faute d’être entretenue,
huilée, la machine humaine elle-même, à s’arrêter.
Les hommes profitent du travail féminin, sans se donner la peine de
penser que l’exploitation de la femme dans le ménage par l’époux,
autorise l’exploitation de la femme par l’employeur.
Les maris, qui ont avili la main-d’œuvre féminine, en établissant
l’usage de ne point la payer, accusent ensuite les femmes de faire baisser
les salaires quand elles apportent, en leurs métiers, l’effort de leurs bras
dont, par la coutume de bénéficier de la gratuité, ils ont reconnu l’indignité
à être récompensée.
L’Etat admet ces malhonnêtes procédés envers le sexe féminin, qu’il
exploite partout où il l’emploie, en lui donnant, pour un travail égal, un
salaire moindre qu’au sexe masculin.
Alexandre Dumas écrivit un jour à une actrice qui lui avait fait des
confidences:
«Méprisez l’homme, passez-vous de lui: toute la force, toute la

valeur de la femme est là!»
En ce conseil est formulé le principe de la liberté féminine. La femme

qui peut exister moralement, matériellement, diriger ses affaires, satisfaire
à ses besoins sans le secours de l’homme, est en dépit de
l’asservissement des lois et des mœurs, son propre maître.
Chose curieuse, les hommes qui, tous se sentent un peu de faiblesse
de caractère, poursuivent la conquête des femmes aptes à endosser leurs
responsabilités. Ils recherchent les fortes qui peuvent se passer d’eux. En
dehors des riches, qui ont toujours été l’objet de leurs convoitises, les
pourvues de bonnes professions ou de réelles aptitudes domestiques
fixent surtout leurs choix. Certes, ils aiment les coquettes, mais seulement
pour flirter!
Cependant, les parents ne tiennent point compte de cette indication. Ils
admirent leurs enfants et attendent tout pour elles de leurs regards
fascinateurs. Les laisseraient-ils dépourvues à la fois, de professions et de
dots? Ils développent chez leurs filles un intensif besoin de luxe. De
même que la riche, la plus pauvre semble devoir être une décorative. Elle
est parée afin de bien affirmer que, seul, un homme très riche pourra
l’entretenir. Parée, à crédit souvent, les industriels escomptent le mariage
des belles filles, comme les usuriers celui des garçons cultivés.
Les institutrices se joignent aux mères idolâtres pour maintenir en
l’erreur, au lieu de les fortifier dans les réalités, les jeunes personnes. Des
éducatrices qualifient les soins du ménage de «besogne de femmes de
charge devant laquelle reculeront les jeunes filles instruites et bien
élevées».
Si, en nos écoles, on éveille de la répugnance pour la première
obligation imposée à toute Française, n’ayant point le moyen de se faire
servir, il ne faut plus s’étonner que le Café reste, comme l’appellait
Théodore de Banville, «Le paradis de la civilisation, l’inviolable refuge de
l’homme contre les poussières et les vulgarités du ménage».
L’éducation et l’instruction ne rendent pas inaptes à se servir soi-
même. Au contraire, tout développement est propice à émanciper du
préjugé qui fait classer le travail en besogne noble ou vile et à le faire
accomplir, ce travail, quel qu’il soit, sans penser déroger.
Un américain millionnaire ne se croit pas déchu, en redevenant cireur
de bottines; voilà pourquoi il remonte si vite au premier échelon social. Il
n’y a guère en France que les juifs qui en tombant de très haut, se
retrouvent sur leurs pieds comme les énergiques Américains.
En conjurant les législateurs de supprimer l’esclavage de la femme qui
entrave la liberté de l’homme, nous supplions les institutrices et les mères
de donner aux Françaises la trempe morale qui les fera libres, parce que
décidées à ne reculer devant aucune besogne, parce que aptes à élever,
en les accomplissant, tous les travaux.
Les jeunes filles instruites, bien élevées, qui n’ont pas le moyen d’avoir
de domestiques ne s’abaissent pas, en se livrant aux soins du ménage,
puisque leur entente de ces occupations leur donne une valeur
nuptialitaire.
Nous connaissons dans différents milieux, des jeunes gens instruits,
distingués, qui, relativement à la dot, ne seront pas exigeants. Seulement
ils veulent trouver chez la compagne de leur vie, du savoir-faire; l’aptitude
à organiser de ses propres mains le bien-être, chez soi.
Ces futurs époux disent: «Nous nous dévouerons avec joie à gagner
entièrement la vie commune, mais à la condition que, pendant que nous
travaillerons, notre compagne ne demeurera pas immobile, en proie aux
dangereuses suggestions de l’oisiveté.»
La femme n’est plus une charge quand elle devient une aide, et l’union
dans l’effort ne saurait déplaire aux jeunes filles fières.
Les jeunes hommes avisés, qui en place d’une dot, demandent à leur
épouse de savoir se servir elle-même, sont inconsciemment des
émancipateurs. Ils forceront mieux que quiconque les jeunes filles à
s’affranchir des besoins fictifs que les préjugés leur ont inculqués et ainsi
à se faire libres, avant de voir décréter leur liberté.
Plus la femme s’évertuera à ne compter que sur elle-même et
s’ingéniera à se passer de l’homme, plus elle sera en condition d’être
recherchée par lui, dans tous les pays parmi toutes les races.
1er mai des Femmes
Quand l’employeur, qui a plus intérêt à rémunérer la besogne

accomplie que les heures de présence au chantier, aura diminué la durée
du labeur quotidien réclamée par les travailleurs des Deux-Mondes[20],
quand l’homme—aristocrate dans l’humanité—sortira à quatre heures de
l’atelier, il pourra, à son gré, se croiser les bras ou se promener comme un
bourgeois, canne à la main. Alors que la femme ouvrière devra toujours,
quelle que soit l’heure à laquelle finisse la journée, entreprendre un travail
encore plus pénible que celui qu’elle vient d’accomplir: balayages,
nettoyages, approvisionnements, cuisinages, lavages, raccommodages,
repassages, soins aux enfants etc., etc.
Les manifestants qui proclament que le 1er mai veut dire: «Plus de
travail exténuant, repos normal, loisir...» ont-ils mis dans leur programme
d’alléger le fardeau de leur compagne en partageant avec elle le travail,
aussi nécessaire qu’improductif, du ménage?
Ce n’est pas, dira-t-on, l’affaire de l’homme de balayer la maison, de
nettoyer les ustensiles, de laver, raccommoder les hardes, de préparer le
dîner.—C’est bon pour une femme de peiner gratuitement dans ces
métiers de femme.
Est-ce qu’il n’y a pas des hommes qui sont valets de chambre,
tailleurs, blanchisseurs, cuisiniers, marmitons?
Lorsqu’il s’agit de gagner de l’argent, l’homme dispute très bien à la
femme l’office de ménager qu’il trouve indigne de lui quand il s’agit d’en
faire la besogne pour rien.
Les mères sont, il faut l’avouer, un peu coupables de leur
exténuement. En négligeant d’apprendre à leurs fils à se servir eux-
mêmes, elles perpétuent, à travers les générations, la tradition du servage
féminin.
Pourquoi l’homme, qui n’a pas au régiment, de domestique pour faire
les corvées, se débarrasse-t-il dans la vie civile, sur sa mère, sur ses
sœurs, sur son épouse, de tout ce qu’il y a de pénible à accomplir dans la
maison?
Astreint, comme la femme, à se nourrir, à user ses vêtements, à salir
son linge, sa vaisselle et son logement, déchoirait-il plus qu’elle, en
balayant, en lavant, en préparant ses aliments, en recousant ses boutons,
comme il le faisait, sans rechigner, à la caserne?—Non! Et avant de
posséder, ou après avoir perdu cette servante gratuite qu’on dénomme
son épouse, l’homme se trouverait fort bien de s’obliger soi-même.
Le partage entre époux du travail du ménage permettrait à la femme
de partager le repos, le loisir de l’homme. Alors en rentrant au logis, le
mari trouverait au lieu d’une femme fatiguée, épuisée, qui a parfois la
bouche amère, une compagne aimable, gracieuse, avec laquelle il serait
fier de se montrer.
Quelle entente mettrait dans le ménage ce simple travail fait ensemble!
Les époux s’entr’aidant en bons camarades, il n’y aurait plus chez la
femme, succombant sous l’effort, la sourde révolte qui se traduit en
humeur. Et chez l’homme, ce serait fini du mépris pour celles auxquelles
sont dévolues des occupations dites serviles—parce que non rétribuées—
puisqu’il partagerait ces occupations.
L’épouse, pas surmenée, conserverait sa gaîté de jeune fille, et, le
mari n’ayant plus à redouter les plaintes et les poussières, se trouverait
heureux dans le logement où grâce à ses muscles, brillerait ce luxe du
pauvre: la propreté.
Quand la Française n’aura plus à supporter que la moitié du fardeau
domestique, elle trouvera enfin le temps de penser qu’elle n’est pas une
bête de somme, qu’elle doit exercer tous les attributs de personne
humaine et s’occuper des intérêts généraux avec lesquels ses intérêts
particuliers ont tant de corrélation.
Les femmes qui sont prises aux entrailles, quand elles entendent des
humains crier—devant des terres où il suffirait de jeter quelques grains
pour que de leurs flancs généreux sorte la nourriture—crier en face de
colonies paradisiaques où les récoltes succèdent aux récoltes: «Je n’ai
pas de travail! j’ai faim!» voudraient réprimer ce désordre social et
assumer avec l’homme la souveraineté publique afin de pouvoir empêcher
la nation de pâtir devant ces richesses inexploitées.
Malheureusement, les femmes sont en même temps que des
dégradées civiques, des condamnées aux travaux forcés à perpétuité.
Les maris, sauf de rares exceptions, croient qu’une épouse est un petit
bœuf donné par la nature et ils usent, ils abusent de son dévouement.
Si la réduction du labeur de l’homme ne devait pas diminuer pour la
femme le surmenage improductif qui fait obstacle à son indépendance
économique, les travailleuses qui peinent souvent dix-huit heures sur
vingt-quatre seraient obligées de se liguer pour faire contre le travail
supplémentaire du ménage qui ne leur rapporte rien, elles aussi, leur 1er
mai.
En se croisant les bras comme eux, devant les travaux domestiques,
les femmes imposeraient aux hommes, habitués à être constamment
servis, des privations qui amèneraient vite leur égoïsme à
accommodement.
Certes, la Française si vive, si active, ne recule pas devant l’ouvrage.
Seulement, elle sait que l’amour, le dévouement, les qualités morales
d’une femme, sont partout moins appréciés que ses charmes, et que, si
elle est enlaidie par d’excessifs labeurs, son mari lui donnera une rivale
plus fraîche. Aussi, pour conserver sa gentillesse et sa santé, c’est-à-dire,
son bonheur en ménage, l’épouse s’insurgera, s’il le faut, contre
l’attribution exclusive qui lui est faite, d’un travail supplémentaire
exténuant.
Mais la femme sera-t-elle forcée de faire son 1er mai, pour éviter de
perdre en se détériorant le cœur de son mari?
Ne serait-ce pas suffisant que ses conseillers à la Tribune et dans la
presse disent à l’homme qui va distraire au cabaret ses heures de
chômage, pendant que sa compagne continue la journée en se tuant de
travail à la maison: «Puisque tu profites du bien-être domestique, fais ta
part de besogne domestique comme au régiment».
Au régiment les hommes sont à tour de rôle astreints à la corvée de
nettoyer la chambrée et à préparer «l’ordinaire»: pourquoi n’en serait-il
pas de même au foyer?
La corvée amicalement partagée entre mari et femme, obligés à se
servir eux-mêmes, semblerait moins pénible. L’effort réciproque pour
rendre l’habitation commune agréable, rapprocherait les conjoints.
Bien plus sages que nous, les Américains reconnaissent que les deux
sexes étant dans l’obligation de se nourrir et de se vêtir, doivent savoir
cuisiner et coudre. Ils font, dans les collèges, suivre en commun par les
garçons et par les filles les cours de cuisine et de couture, afin qu’en
l’épreuve de la vie hommes et femmes soient pareillement aptes à se
rendre, à l’occasion, à eux-mêmes, services.
Quand s’inspirera-t-on dans les écoles de France de ce bon exemple
Américain?
Qui fera le ménage?
Comme les jeunes filles, les jeunes gens ont besoin d’être initiés aux
arts domestiques.
—Qui fera demain le ménage?
—Celui des époux qui sera le plus savant!
«Celui de nous deux, dit Socrate, glorifiant le travail du
ménage, qui sera le plus industrieux économe, est celui qui
apporte le plus en la société.»
Que l’on ne se hâte point de sourire. Avant de réfuter ces affirmations,

il est bon d’examiner si un intérêt supérieur n’exige pas, que soit remonté
le courant d’anarchie sociale où tout est bouleversé, déplacé, où nulle
chose n’est appréciée selon sa valeur, où nul être n’est, d’après son
mérite, coté.
En notre société où un commis de magasin est mieux vu que
l’indispensable semeur de blé, où les professions sont d’autant moins
rétribuées et considérées qu’elles sont plus utiles, où l’on gagne
davantage à amuser les êtres qu’à décupler leur existence, où il y a
l’académie de musique et pas l’académie de l’alimentation, il n’est point
surprenant que le sexe masculin défende ses positions honorées, parce
que lucratives, et ne veuille participer aux travaux, qualifiés de vils, parce
que pas rémunérés.
Quand se dissiperont les ténèbres qui voilent aux humains la vérité?
Les arts domestiques, dont peut résulter la modification des êtres, seront
recherchés, réhabilités. Si l’on ne crée pas comme le proposent des
gastronomes, une académie de femmes gardiennes de l’art de bien vivre,
on peut être certain que les générations futures se préoccuperont de vivre
pleinement, en complète santé et que selon le vœu du baron Brisse, sera
installée à Paris une faculté de chimie culinaire, et que la science de
l’alimentation enseignée gratuitement fera baisser la mortalité.
Présentement, les humains ont moins que les animaux, l’instinct de la
conservation.
Dans les écoles on apprend tout aux enfants, hormis l’art d’augmenter
l’énergie vitale.
Mais viendra l’heure où chacun ayant la science de la conservation,
s’évertuera à renouveler ses forces pour prolonger son existence. Alors,
l’ensemble des travaux qui coopèrent à ce résultat, apparaîtra de premier
ordre, sera le plus relevé. Les êtres instruits et intelligents ne se
déchargeront plus sur quiconque, à la maison, des soins que le savant se
réserve à lui-même dans le laboratoire.
On a déjà, de cela, des signes précurseurs. Lorsque les femmes
demandent à contrôler l’emploi de l’argent qu’elles versent, comme
contribuables, chez le percepteur; et que les malotrus leur crient:—Votre
place est à la cuisine; retournez à vos casseroles! elles ne se sentent
point insultées et regardent d’un gentil air de pitié leurs insulteurs. On
croirait qu’elles ont compris:—Votre place est au laboratoire! Retournez à
vos cornues!
Tout le monde a aujourd’hui l’intuition de cuisines savantes, on
pressent que les casseroles méprisées deviendront les philtres, en
lesquels on puisera le secret de vie, l’élargissement intellectuel.
L’humain possédant la science de la conservation, substituera à la
médication inoffensive ou corrodante, l’alimentation scientifique qui
favorisera le libre jeu de tout l’organisme. En ce temps-là, on traitera
d’égaux les préparations de bouillons régénérateurs et les
confectionneurs de bouillons de culture. Le cuisinier sera un savant
comme le savant est un cuisinier.
Bien que les tranches de pain coupées en rond ne doivent plus,
comme autrefois, servir d’assiettes, que restera-t-il à ce moment de la
vulgarité du ménage?—Pas même les poussières que Banville conseillait
de fuir en allant au café.
Hommes et femmes se disputeront les prérogatives qui leur
permettront de rendre beaux les laids, vigoureux les faibles, avec un
atome de substance ferme et fluide.
Comme en la parant de la couleur seyante on fait s’affirmer la beauté,
en adaptant au tempérament de chaque individu les sucs nourriciers
appropriés, on décuplera la vigueur physique et intellectuelle, on fera
s’affirmer la santé. On peut donc prédire le triomphe des manieurs de
casseroles où s’élaboreront les mixtures vivifiantes.
Pour le moment, la cuisine est désertée et ce qu’on y fait est qualifié
d’œuvre vile, ne méritant pas d’être rémunérée. Un politicien malade
n’existant que grâce à sa ménagère, a même, en parlant des salaires,
avancé cette énormité qui synthétise les erreurs contemporaines:—Il
tombe sous le sens que le travail d’une ménagère a moins de valeur
sociale que celui d’un mécanicien, d’un employé.
Mais la ménagère est le premier des mécaniciens, puisqu’elle
entretient en un bon état de fonctionnement, la machine de chair humaine
autrement précieuse que celle de métaux que la vapeur met en
mouvement. Car à quoi serviraient toutes les autres machines, si celle-ci
d’abord n’existait?
C’est l’absence du sentiment de sa propre conservation qui fait
mépriser par l’homme les travaux dont la prolongation de l’existence peut
résulter.
L’aristocratie de sexe qui a succédé à celle de caste ne permet pas
aux mâles de se livrer aux occupations ménagères; c’est travail vil, parce
que improductif.
Pourtant, bien que l’on ne sache commander que ce que l’on sait
exécuter, ces mêmes hommes qui trouvent l’art ménager au-dessous
d’eux, se sont réservé le droit d’élaborer le programme du cours ménager
voté par le Conseil Municipal, et ils brevèteront aussi le savoir ménager,
puisqu’il y aura à faire cela, honneurs et profits pour eux.
L’homme ne veut pas sans être rémunéré, s’utiliser; même celui qui a
pour métier de servir les autres, feint en rentrant chez lui, de ne pas savoir
se servir lui-même.
C’est l’ignorance et le préjugé qui font considérer comme abjects les
travaux de premier ordre. La science de la conservation humaine
exhaussera les arts domestiques.
Demain on honorera les inventeurs de mets réparateurs, comme on
honore aujourd’hui les inventeurs d’engins meurtriers.

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Atomic and Nano Scale Materials for

Advanced Energy Conversion, Volume

Edited by Zongyou Yin

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Part I Emerging Nanomaterials for Electrochemical (EC)

2 2D-Materials-Free Heterostructures for EC Energy

2.3.2 Metal/Heteroatom-Doped Porous Carbon-Based Heterostructures 39

3 2D-Materials-Based Heterostructures for EC Energy

4 Superlattices for EC Energy Conversion 129

5 Polymorphic Phase Engineered Structures (PPESs) for EC

6 Rare-earth Nanomaterials for EC Energy Conversion 171

Part II Emerging Nanomaterials for Photochemical (PC)

7 2D-Materials Free Heterostructures for photochemical Energy

7.1.2 PC CO2 Reduction Reaction 207

8 Van der Waals Heterostructures in Photocatalytic Energy

9 Superlattices for PC Energy Conversion 275

10 Polymorphic Phase Engineered Structures (PPESs) for PC

11 Rare-earth Nanomaterials for PC Energy Conversion 309

12 Non-noble Plasmonic Enhancement (NNPE) for PC Energy

12.3 NNPE CO2 Reduction Reaction (CRR) 331

Part III Emerging Nanomaterials for Photoelectrochemical

13 2D Materials-Free Heterostructures for PEC Energy

14 2D-Materials-based Heterostructures for PEC Energy

14.4.1.3 2D/2D Heterostructures 374

15 Polymorphic Phase Engineered Structures (PPES) for PEC

16 Rare-earth Nanomaterials for PEC Energy Conversion 399

17 Non-Noble Plasmon Enhancement (NNPE) for PEC Energy

Part IV Emerging Nanomaterials for Photovoltaic (PV)

18 2D-Materials Free Heterostructures for Photovoltaic Energy

19 2D-Materials-based Heterostructures for PV Energy

20 Perovskite–Si Tandem Solar Cells 481

21 III–V Compound Semiconductor Nanowire Solar Cells 531

22 Rare-Earth Nanomaterials for PV Energy Conversion 559

23 Non-noble Plasmon Enhancement (NNPE) for PV Energy

Part V Clusters for Energy Conversion 611

24 Electrochemical Energy Conversion with Clusters 613

25 Photochemical Energy Conversion with Clusters 655

26 Photoelectrochemical Energy Conversion with Clusters 695

Part VI Single Atoms for Energy Conversion 719

27 Electrochemical Energy Conversion with Single Atoms 721

28 Photochemical Energy Conversion with Single Atoms 773

29 Photoelectrochemical (PEC) Energy Conversion with

30 Future Perspectives 815

3. Polymorphic phases of solid materials, such as crystal structural phases, single-

Emerging Nanomaterials for Electrochemical (EC) Energy

2D-Materials-Free Heterostructures for EC Energy

2.1 Heterostructures for Electrochemical Water Splitting

Electrochemical water splitting is largely considered a highly efficient protocol

2.1.1 Metal Oxide-Based Heterostructures

Table 2.1 Recent advances in nonprecious metal-based nano-heterostructured electrocatalysts for

Metal oxides CuCo@CuCoOx HER Support: NFa) 𝜂 10 : 112 mVc) [4]

Table 2.1 (Continued)

Co@Ni3 N HER Electrode: CCk) 𝜂 10 : 194 mV [10]

Table 2.1 (Continued)

Ni3 S2 @Ni-Fe-OH OER Electrode: NF 𝜂 10 : 165 mV [16]

(b) IrO2 0.40