Response To Reviewer Comments

Response to Reviewer Comments: (Manuscript Number: RSER-D-22-04203)
Dear Editor,
Renewable and Sustainable Energy Reviews
We appreciate your kind consideration and the reviewers for providing their valuable
comments/suggestions to improve the quality of our recent submission
for the consideration of publication by Renewable and Sustainable Energy
Reviews. According to the given comments, we have thoroughly revised the manuscript. We
hope this revision can meet the reviewers' and your requirements. The followings are our
point-by-point responses:
Editorial Points:
1. Submit the original manuscript showing clearly all textual changes using track changes.
Just highlighting textual changes in yellow (or other colour) is not acceptable. This
includes all edits related to reviewer(s) comments and the Editorial points.
Response: Based on the editor’s comments, we have updated the original manuscript using
track changes for all responses to the reviewer’s comments.
2. Submit the clean revised version of the manuscript.
Response: As per the editor mentioned, we have submitted the carefully revised version of
the manuscript with appropriate response to the reviewer’s comments.
3. Provide a 'Response to reviewers and Editor document' with a point by point response to
each comment from the reviewer(s) and the Editor (i.e. points 1 to 7). Carefully and fully
address the issues raised and refer to each comment from the reviewer(s) and the Editor
clearly in the revised/edited/changed text in the marked-up copy of the original manuscript
(e.g. line number X to Y on page X in the marked-up manuscript) in this response.
Response: Based on the editor’s comment, we have submitted the carefully revised version
of the manuscript with appropriate response to the reviewer’s comments. We have mentioned
the appropriate line number and page number of the manuscript in the Response to Reviewer
Comments file.
4. Read the 'Guide for Authors' at https://www.elsevier.com/journals/renewable-and-
sustainable-energy-reviews/1364-0321/guide-for-authors very carefully. It is the sole
responsibility of the author(s) to ensure that their article is correct and meets RSER style
and format fully in terms of contents and layout (e.g. authorship, order of authorship,
addresses, article structure, keywords, abbreviations, nomenclature, captions on figures
and tables, acknowledgement of those that helped and or funded the research including
datasets, references).
Response: As per the editor mentioned, we have followed the RSER style with the contents
and layout format as mentioned in the Guide for Authors.
5. Ensure that permission is attained for all copyrighted graphics, images, tables and/or
figures. Note that for any figures, graphics or images published elsewhere by the author or
others, the author(s) must arrange permission and this must be clearly stated in the
'Acknowledgements' section at the end of the article. If the author(s) cannot arrange
permission, then the graphics, images, tables and or figure must be removed from the
manuscript.
Response: As per the editor mentioned, we have collected copyrights permission for all the
mentioned figures, graphics, and images in the manuscript.
6. Check the English carefully for grammar, spelling and syntax. This is an English language
journal. It is also not the role of reviewer(s), the Editor or indeed the publishing team to
proof read the English, grammar and or syntax of a manuscript. The function of the
reviewer(s) and an editor is to examine scope, robustness and technical content. Proof
reading is the sole responsibility of the author(s), for example, articles are written in the
first or third person and the use of "I," "we" or "they" should be avoided. Note if an article
is revised and resubmitted with poor English, grammar and or syntax it will be rejected.
Author(s) should get help from a colleague with better English, or alternatively a paid
English language editing service of which there are many, could be arranged. For
example, Elsevier offers author-paid language editing services via the Author Webshop,
see http://webshop.elsevier.com/languageediting However, using an English language
service (including Elsevier's) is NOT a guarantee that an article will be subsequently
accepted for publication.
Response: As per the editor mentioned, we have carefully check the manuscript for
grammatical errors and typos. We have removed the first person statement, “we”, from the
manuscript.
7. Check your manuscript for intentional or unintentional plagiarism of your own work or
work by others elsewhere. All author(s) must read 'Ethics in publishing' in the 'Guide for
Authors' and 'Publishing Ethics' at
https://www.elsevier.com/about/our-business/policies/publishing-ethics and 'Ethical
guidelines for journal publication' at

https://www.elsevier.com/authors/journal-authors/policies-and-ethics The policy of RSER
is to publish new and original work. Text, even in introductions, is the intellectual property
of the original publication, and should never be used without clearly distinguishing that it
is from another source (either by quotations or indentations). Author(s) cannot also reuse
or recycle some (or indeed all) of their work published elsewhere as it is already covered
by copyright. Each article should present some novelty and new result, and it is the
Editor's opinion that this should be written in the author(s) own words. Unless the
author(s) have a legitimate explanation for the large amount of textual overlap between
their submitted manuscript and previously published work(s), an article will not be
considered further for publication. All manuscripts submitted to RSER are checked for
originality using the CrossRef Similarity Check database. For more information on
CrossRef visit their website at http://www.crossref.org/crosscheck.html
Response: As per the editor mentioned, we have carefully checked the manuscript for
plagiarism following the read 'Ethics in publishing' in the 'Guide for Authors' and 'Publishing
Ethics'.
Reviewer #2:
1. Introduction section: The recent statical data of supply and demand of hydrogen
production to be include in this section.
Response: We thank the reviewer for the valuable comment. As per the reviewer’s comment,
we included the recent statical data of supply and demand of hydrogen production in the
introduction section. Currently around 95% of the world’s total hydrogen (H2) production is
achieved by natural gas, steam reforming or other fossil fuels, which required high
temperature and pressure. The global hydrogen energy requirement has achieved 94 Mt in
2021 which is a 5% increase than in 2020 [2]. Predictions show that in 2030 hydrogen energy
demand would reach 180 Mt that benefits the heavy industry, hydrogen-based fuels and
power generation [2]. Currently, 75 Mt of pure H 2 and 45 Mt of mixed gases with H 2 is
produced per year [3]. The global hydrogen market will grow from $142 billion in 2019 to
$209 billion in 2027. However, 95% of the hydrogen produced are from fossil fuels which
result in pollution [4]. The green and sustainable hydrogen generation allows for a low-cost
and highly efficient technology that is crucial for deployment of the hydrogen economy at the
terawatt scale [4]. Otherwise, it is not possible for green hydrogen to compete with grey
hydrogen from fossil fuel (ex. Methane reforming). Electrochemical water splitting as a
promising hydrogen production method attracted great interest in the past decades [5, 6].
The above-mentioned changes have been updated in the revised manuscript Page 8, line 8.
References:
[1] IEA. Hydrogen. 2022 [cited 2023 January 5]; Available from:
https://www.iea.org/reports/hydrogen.
[2] Vesborg PCK, Jaramillo TF. Addressing the terawatt challenge: scalability in the supply
of chemical elements for renewable energy. RSC Advances 2012;2(21):7933-47.

[3] IRENA. Hydrogen. [cited 2023 January 5]; Available from:
https://www.irena.org/Energy-Transition/Technology/Hydrogen.
[4] Chatenet M, Pollet BG, Dekel DR, Dionigi F, Deseure J, Millet P, Braatz RD, Bazant
MZ, Eikerling M, Staffell I, Balcombe P, Shao-Horn Y, Schäfer H. Water electrolysis: from
textbook knowledge to the latest scientific strategies and industrial developments. Chemical
Society Reviews 2022;51(11):4583-762.
[5] Yan Y, Xia BY, Zhao B, Wang X. A review on noble-metal-free bifunctional
heterogeneous catalysts for overall electrochemical water splitting. Journal of Materials
Chemistry A 2016;4(45):17587-603.
[6] Hu C, Zhang L, Gong J. Recent progress made in the mechanism comprehension and
design of electrocatalysts for alkaline water splitting. Energy & Environmental Science
2019;12(9):2620-45.
2. Figure 2 should be further elaborated in text.
we have provided a detailed explanation of Fig. 2R1. The polarization curves of OER, AOR,
and HER can be seen in the Fig.2, indicating that OER requires higher overpotentials to reach
the same current density as AOR. The polarization curve of OER, AOR, and HER can be
seen, indicating that OER requires higher overpotentials to reach the same current density as
AOR [11]. The potential determining steps (Eqn 4 and Eqn 5) are the elementary reaction
steps that affects the thermodynamic overpotential [2]. When the Gibbs free (ΔG)
chemisorption energy increases between two successive adsorbed intermediates, the potential
is limited for the further reaction steps. Due to the long-standing scaling relationship between
the free energy of formation for *OH and *OOH, a high potential becomes essential for the
critical potential determining step (PDS). Thus, there is a minimum potential value of 1.23 V
for OER to initiate reactions at the anode. The scaling relations for the adsorption of
intermediates and the PDS for OER are the major limitation for OER activity which result in
a high theoretical potential of 1.23 V [3].
M-OH + OH¯ → M-O + H2O (1)
2M-O → 2M + O2(g) (2)
Fig. R1.2. The comparison of various anode reaction potentials in the water electrolysis
system.
AOR of chemical species involves low theoretical potential and is aimed to generate
sustainable hydrogen and value-added products produced in the hybrid water electrolysis
technology. There is also a notable difference between the steps involved in OH insertion in
OER and AOR. OER forms the O-O bond on the catalyst surface by forming oxo- and/or
peroxo-species. As aldehyde oxidizes to carboxylic acid, geminal diol (-OH bound to the
same carbon) forms, leading to a rise in oxygen concentration. This process does not involve
oxygen species adsorption on catalyst surfaces or electrochemical reactions. The formed
geminal diol is then oxidized to carboxylic acid [4]. This process is like the dehydrogenation
of alcohol to aldehyde. Therefore, OER and AOR do not have the same dehydrogenation or
oxygen insertion steps [5]. The organic oxidation of alcohol and N-containing molecules,
such as ammonia, hydrazine, and urea are widely available and possesses a lower theoretical
oxidation potential, which contributes to a lower overall reaction voltage than water splitting
[6].
In this system, biomass-derived aldehyde oxidation platform chemicals such as 5-
hydroxymethyl furfural (HMF), glucose, and furfural are particularly appealing because the
both electricity used and organic essential feeds are renewable, making the H 2 production
process sustainable [7]. The AOR involve the electrocatalytic conversion of aldehydes to
corresponding carboxylate and hydrogen on the electrocatalyst at low onset potential. The
hydrogen production for a conventional organic electrolysis system still required a high
voltage input of (˃1 V), resulting in this system’s high electricity consumption [1]. Therefore,
organic oxidation and aldehyde oxidation require lower potential in this system compared to
OER shown in Fig. 2R1.
The above-mentioned changes have been updated in the revised manuscript. Page 18,
Line 21.
References:
[1] Wang T, Tao L, Zhu X, Chen C, Chen W, Du S, Zhou Y, Zhou B, Wang D, Xie C, Long
P, Li W, Wang Y, Chen R, Zou Y, Fu X-Z, Li Y, Duan X, Wang S. Combined anodic and
cathodic hydrogen production from aldehyde oxidation and hydrogen evolution reaction.
Nature Catalysis 2022;5(1):66-73.
[2] Fu X, Wan C, Huang Y, Duan X. Noble Metal Based Electrocatalysts for Alcohol
Oxidation Reactions in Alkaline Media. Advanced Functional Materials
2022;32(11):2106401.
[3] Dau H, Limberg C, Reier T, Risch M, Roggan S, Strasser P. The Mechanism of Water
Oxidation: From Electrolysis via Homogeneous to Biological Catalysis. ChemCatChem
2010;2(7):724-61.
[4] Bender MT, Yuan X, Choi K-S. Alcohol oxidation as alternative anode reactions paired
with (photo)electrochemical fuel production reactions. Nature Communications
2020;11(1):4594
[5] Liu J, Wang Y. Theoretical identification and understanding of catalytic active sites for
water splitting reactions. Catalysis: Volume 34: The Royal Society of Chemistry; 2022. p. 1-
16.
Chemistry A 2016;4(45):17587-603.
[7] Artero V, Chavarot-Kerlidou M, Fontecave M. Splitting Water with Cobalt. Angewandte
Chemie International Edition 2011;50(32):7238-66.
3. There are some typo mistakes in this manuscript. Please have a check throughout the
manuscript.
we have corrected the typo mistakes in the revised manuscript.
4. Page 55, Lines 1-2, section 5.6.2.: please provide supporting from literature to support this
statement ‘Renewable biomass derivatives can help increase energy demands and improve
infrastructure sustainability by converting them into commercially relevant compounds.
Response: We thank the reviewer for pointing out the mistake in the mentioned statement.
We apologize for the mistake and as per the reviewer’s comment, we have attached the
reference in the revised manuscript. Conversion of renewable biomass derivatives to

commercial applicable compounds can contribute to the sustainable infrastructure
development and meet rising energy demands. In addition to the numerous chemical
applications, furfural is a promising biomass-derived synthetic platform species to produce
furoic acid, furanone, maleic anhydride, succinic acid, and malic acid [1]. The partial
oxidation of furfural yields products such as furanone, acid anhydride, and dicarboxylic acid
with increasing molar ratio of oxygen to carbon [2, 31, 2].
The above-mentioned changes have been updated in the revised manuscript Page 65, Line
8..
References:
1. Li G, Naveen A, Alex R, Adam H, Michael J, Density functional theory study of furfural
electrochemical oxidation on the Pt (111) surface. Journal of Catalysts,2019.373: p.322-
335.
2. Liu Q, Li MY, Shi MY, Liu CB, Yu YF, Zhang B. In situ structural reconstruction of
NiMo alloy as a versatile organic oxidation electrode for boosting hydrogen production.
Rare Metals, 2022. 41(3): p. 836-843.
5. Graphical abstract needs further improvement to draw out the significances of this review
paper.
we have corrected the graphical abstract in the revised manuscript.

Fig. R2. Graphical abstract representing prospects of anode oxidation and hybrid water
electrolysis.
The above-mentioned changes have been updated in the revised manuscript Page, 03.
Reviewer #3:
1. Page 6, Line 12-13, NO should be the abbreviation of “Nitrogen oxide”? Please check the
manuscript very carefully to avoid similar errors.
Response: We thank the reviewer for the valuable comment. As per the reviewer’s
suggestion, we carefully revised the manuscript to avoid the above-mentioned errors.
5.
2. Page 7, the second paragraph. It seems the author wanted to show two advantages of
AOR over OER, i.e. the lower potential and no gas mixing. However, the two advantages
were mixed up. The paragraph should be revised to make it clear and more logically
accessible to readers.
we included the advantages of AOR. In recent years, hybrid water electrolysis systems have
been developed rapidly, which offer many advantages over conventional water electrolysis
systems as listed below.
1. Electrochemical water splitting for highly efficient hydrogen (H 2) production can be
improved with AOR due to low potential requirement at the anode. By utilizing low-cost
reductive chemical additives, like Urea, alcohol, and aldehydes, as sacrificial agent to
substitute for the kinetically sluggish OER, which can greatly lower the cell voltage input
of energy consumption [1].
2. In this system, high value-added products, instead of O 2, can be expected to produce at the
anode side of the system by choosing suitable feedstock chemicals and maximizing the
return of energy investment [2].
3. The hybrid water electrolysis system could lower the voltage input and exclude the
formation of H2/O2 gas mixture and reactive oxygen species due to the replacement of
OER with thermodynamically more favorable AOR [2].
5.
References:
[1] Li Y, Wei X, Han S, Chen L, Shi J. MnO2 Electrocatalysts Coordinating Alcohol
Oxidation for Ultra-Durable Hydrogen and Chemical Productions in Acidic Solutions.
Angewandte Chemie International Edition 2021;60(39):21464-72.

2020;11(1):4594.
3. Page 7, line 55-60. How the chemical were chosen for AOR? The principle of chemical
selection should be elaborated here before giving the samples.
suggestion, we include the principle of chemical selection.
Feedstock chemical choice for AOR
There are some key criteria involving the feedstock chemical that should be considered
when selecting an oxidation reaction to replace OER. Several requirements should be met to
establish an energy-saving hybrid water electrolysis.
[1.] The AOR requires water soluble chemicals at room temperature, which oxidizes at low
potentials than OER. [1, 2]
1.[2.] The feedstock chemicals for the AOR should have potential to be transformed into
value-added products so that achieving the hydrogen production at cathode side by a more
cost-effective pathway [1].
2.[3.] Furthermore, the chosen anodic chemicals should have negligible competition with the
cathode side HER [1].
3.[4.] Specific value-added products can be produced by an appropriate choice of oxidative
species. For example, furfural, HMFCA, and furoic acid can be specifically produced by
anodic oxidation of HMF depending on the number of electron transfer steps [2].
Similarly, nitric acid and formic acid are the oxidative reaction products of N 2 and
glycerol, respectively [3, 4].

The above-mentioned changes have been updated in the revised manuscript Page 17,
Line 10.
References:
[1] Deng C, Toe CY, Li X, Tan J, Yang H, Hu Q, He C. Earth-Abundant Metal-Based
Electrocatalysts Promoted Anodic Reaction in Hybrid Water Electrolysis for Efficient
Hydrogen Production: Recent Progress and Perspectives. Advanced Energy Materials
2022;12(25):2201047.
[2] Wang T, Tao L, Zhu X, Chen C, Chen W, Du S, Zhou Y, Zhou B, Wang D, Xie C,
Long P, Li W, Wang Y, Chen R, Zou Y, Fu X-Z, Li Y, Duan X, Wang S. Combined
anodic and cathodic hydrogen production from aldehyde oxidation and hydrogen
evolution reaction. Nature Catalysis 2022;5(1):66-73.
[3] Wang Y, Li T, Yu Y, Zhang B. Electrochemical Synthesis of Nitric Acid from
Nitrogen Oxidation. Angewandte Chemie International Edition 2022;61(12):e202115409.
[4] Ottoni CA, da Silva SG, De Souza RFB, Neto AO. Glycerol oxidation reaction using
PdAu/C electrocatalysts. Ionics 2016;22(7):1167-75.
4. Scheme 1. What are the meaning of :0.37V, 0.55-0.66 V, etc. ” in the scheme? The value
of “Nitrogen oxidation” was missing. In addition, the values no the arrow is also
confusing. More explanations should be given in the scheme or the legend.
we have revised the manuscript.
Fig. R3a demonstrates the electro-oxidation reaction mechanism of various chemical
species in hybrid water electrolysis. The thermodynamical potential requirement for urea
electrolysis is comparatively less than required for OER. Furthermore, urea is globally
sufficient in human urine, urea-rich wastewater, and as a by-product of industrial activities.
The two-stage urea oxidation reaction (UOR) pathway involves the production of
intermediate ammonia and the subsequent decomposition of that ammonia to nitrogen (N 2).
As a result, the different rate-determining steps with favorable thermal/kinetic energetics
achieves a high current density at comparatively lower potentials than in conventional OER
[1-9].
The alcohol oxidation theoretical potential is 0.5 - 1.3 V (vs. SCE). The oxidation of
various alcohols (e.g., ethanol, methanol, and glycerol) are used to substitute OER, and these
alcohols were decomposed into value-added products. The cathode hydrogen production is
promoted at a lower potential than at the anode [10-18].
Scheme 1.Fig. R3. (a) Schematic representation of electro-oxidation of various chemical
species and (b) their respective theoretical potentials in various electrolysis technologies
based on previous reports. (b) Scheme representing the previously reported onset potentials
for various oxidative species under different electrocatalysts [2-24]. The arrow represents the
increasing works on hybrid water electrolysis technology to achieve high efficiency.
The next strategy is nitrogen oxidation reaction (NOR), more importantly
electrochemical cells require only ambient N2 and water as feedstock, making the electrolysis
very promising and cost-effective. The NOR equilibrium potential of 1.08 V vs RHE, and the
resultant product, nitrate is crucial to produce fertilizers, gunpowder, and explosives, which
plays an important role in our current society [19-21].
The biomass-derived aldehyde oxidation potential is <0.5 - >1.0 V vs. RHE. In this
platform, chemicals such as 5-hydroxymethyl furfural (HMF), glucose, and furfural are
particularly appealing because both the organic feeds used and the electricity are renewable,
making the hydrogen (H2) production process sustainable [21-25]. Fig. R3b shows the
previously reported electrocatalysts with corresponding onset potentials for various anode
oxidation reactions [2-24]. Hence, developing highly efficient oxygen evolution
electrocatalyst is essential to enhance the activity towards AOR. Several crucial strategies
have been followed to increase the efficiency and commercialization of the hybrid water
electrolysis technology, such as electrolyte engineering, membrane technology, electrolyzer
design, and electrocatalyst engineering. Hence, the emerging field of hybrid water
electrolysis system for efficient electrochemical hydrogen production and generation of
value-added products becomes remarkably functional.
The above-mentioned changes have been updated in the revised manuscript Page 8, Line 11.
References:
1. Shi-kui G, Yao Z, Shan-qing L, Hui S, Xu Z, Jun H, et al. Nickel ferrocyanide as a high-
performance urea oxidation electrocatalyst. Nat Energy, 6, (2021) 904-912.
2. Lu XF, Zhang SL, Sim WL, Gao S, Lou XW. Phosphorized CoNi2S4 Yolk-Shell Spheres
for Highly Efficient Hydrogen Production via Water and Urea Electrolysis. Angewandte
Chemie International Edition, 2021. 60(42): p. 22885-22891.
3. Ji X, Zhang Y, Ma Z, Qiu Y. Oxygen Vacancy-rich Ni/NiO@NC Nanosheets with
Schottky Heterointerface for Efficient Urea Oxidation Reaction. ChemSusChem, 2020.
13(18): p. 5004-5014.
4. Liu G, Huangh C, yang Z, Su J, Zhang W. Ultrathin NiMn-LDH nanosheet structured
electrocatalyst for enhanced electrocatalytic urea oxidation. Applied Catalysis A: General,
2021. 614: p. 118049.
[5.] Patil SJ, Chodankar NR, Hwang, Ganji Seeta Rama Raju, Huh YS, Han YK. Fliuorine
Engineered Self-Supported ultrathin 2D Nickel Hydroxide nanosheets as Highly Robust
and stable Bifunctionasl Electrocatalysts for oxygen Evolution and urea Oxidation
Reactions. Small, 10.1002/small.202200832,18,24,2022.
5.[6.] Min Z, Jinghua W, Zhiyun L, Haihong W, Jinling W, Hualin W, Lin H, and Xuejing Y.
Interlayer Effect in NiCo Layered Double Hydroxide for Promoted Electrocatalytic Urea
Oxidation. ACS Sustainable Chem. Eng. 2019,7,5, 4777-4783.
6.[7.] Wu N, Guo R, Zhang X, Gao N, Chi X, Cao D, Hu T. Nickel/nickel oxide nanocrystal
nitrogen-doped carbon composites as efficient electrocatalysts for urea oxidation. Journal
of Alloys and Compounds, 2021. 870: p. 159408.
7.[8.] Wang K, Huang W, Cao Q, Zhao Y, Sun X, Ding R, Lin W, et al. Engineering
NiF3/Ni2P heterojunction as efficient electrocatalysts for urea oxidation and splitting.
Chemical Engineering Journal, 2022. 427: p. 130865.

8.[9.] Zhang C, Du X, Zhang X. Controlled synthesis of three-dimensional branched Mo–
NiCoP@NiCoP/NiXCoYH2PO2 core/shell nanorod heterostructures for high-performance
water and urea electrolysis. International Journal of Hydrogen Energy, 2022. 47(20): p.
10825-10836.
9.[10.] Munde AV, Mulik BB, Chavan PP, Sapner VS, Narwade SS, Mailo SM, Sathe BR.
Electrocatalytic Ethanol Oxidation on Cobalt–Bismuth Nanoparticle-Decorated Reduced
Graphene Oxide (Co–Bi@rGO): Reaction Pathway Investigation toward Direct Ethanol
Fuel Cells. The Journal of Physical Chemistry C, 2021. 125(4): p. 2345-2356.
10.[11.] Meng X, Ouyang Y, Wu H, Huang H, Wang F, Wang S, et al. Hierarchical defective
palladium-silver alloy nanosheets for ethanol electrooxidation. Journal of Colloid and
Interface Science, 2021. 586: p. 200-207.
11.[12.] Qiu Y, Zhang J, Jin J, Sun J, Tang H, Chen Q, et al. Construction of Pd-Zn dual sites
to enhance the performance for ethanol electro-oxidation reaction. Nature
Communications, 2021. 12(1): p. 5273.
12.[13.] Ming Z, Jiawei L, Chongyi L, Yiyao G, Bo C, Chaoliang T, Thanxi F, Jingtao H, et
al. Synthesis of Pd3Sn and PdCuSn nanorods with L12 Pkase for Highly Efficient
Electrocatalytic Ethanol Oxidation. Adv. Mater, 2022,34, 2106115.
13.[14.] Gómez AR, Lepre E, Silva LS, Salas NL, Osa ARDL. PtRu nanoparticles supported
on noble carbons for ethanol electrooxidation. Journal of Energy Chemistry, 2022. 66: p.
168-180.
14.[15.] Dongming Z, Junjun Z, Haoyu W, Can C, Weizhou J, Jing G, YouZhi L. Novel Ni
foam based nickel oxalate derived porous NiO nanostructures as highly efficient
electrodes for the electrooxidation of methanol/ethanol and urea. Journal of Alloys and
Compounds 806, 2019, 1419-1429.

15.[16.] Lignesh D, Arthi G, and Sushmee B. Highly Stable NiCoZn ternary Mixed-Metal-
Oxide Nanorods as a Low-Cost, Non-Noble Electrocatalyst for Methanol Electro-
Oxidation in Alkaline Medium. Energy Fuels 2021, 35, 15, 12507-12515.
16.[17.] Sengeni A, Hisashi S, and Suguru N. Ultrafast Growth of a Cu(OH)2-CuO
Nanoneedle Array on Cu Foil for Methanol Oxidation Electrolysis. ACS Appl. Mater.
Interfaces 2020, 12, 24, 27327-27338.
17.[18.] Jiang YC, Sun HY, Li YN, He JW, Tian X, Li FM, et al. Bifunctional Pd@RhPd
Core–Shell Nanodendrites for Methanol Electrolysis. ACS Applied Materials &
Interfaces, 2021. 13(30): p. 35767-35776.
18.[19.] Dai C, Sun Y, CHen G, Fisher AC, Xu ZJ. Electrochemical Oxidation of Nitrogen
towards Direct Nitrate Production on Spinel Oxides. Angewandte Chemie International
Edition, 2020. 59(24): p. 9418-9422.
19.[20.] Wang D, He N, Xiao L, Dong F, Chen W, Zhou Y, Chen C, Wang S. Coupling
Electrocatalytic Nitric Oxide Oxidation over Carbon Cloth with Hydrogen Evolution
Reaction for Nitrate Synthesis. Angewandte Chemie International Edition, 2021. 60(46):
p. 24605-24611.
20.[21.] kuang M, Wang Y, Fang W, Tan H, Chen M, Yao J, et al. Efficient Nitrate Synthesis
via Ambient Nitrogen Oxidation with Ru-Doped TiO 2/RuO2 Electrocatalysts, Adv.
Mater.2020,2002189.
21.[22.] Liu Q, Li MY, Shi MY, Liu CB, Yu YF, Zhang B. In situ structural reconstruction of
NiMo alloy as a versatile organic oxidation electrode for boosting hydrogen production.
Rare Metals, 2022. 41(3): p. 836-843
22.[23.] Li Y, Ding J, Liu X, wang J, Jiao S, Kang N, Li J, Irfan M, Zhang P. Physically
mixed Ni2Co/graphene catalyst for enhanced glucose oxidation in a glucose fuel cell.
Biomass Conversion and Biorefinery, 2022.

23.[24.] Huang S, Li J, Chen Y, Yan L, Zhang P, Zhang X, Zhao C. Boosting the anti-
poisoning ability of palladium towards electrocatalytic formic acid oxidation via
polyphosphide chemistry. Journal of Colloid and Interface Science, 2022. 615: p. 366-374.
24.[25.] Tehua W, Li T, Xiaorong Z, Chen C, Wei C, Shiqian D, et al. Combined anodic and
Nature Catalysis 5, 66-73 (2022).
5. Page 9, line 2-20. The classification of electrocatalysts have been mentioned many time
the in manuscript (as in abstract, introduction, section 4 and conclusion), but the
classification was not consistent in all these parts. Please check the manuscript carefully
to make the statement consistent.
Response: We thank the reviewer for the valuable comment. As per the reviewer’s comment
we corrected the classification of electrocatalyst, in abstract, introduction, section 4, and
conclusion.
In abstract - Besides, This review summarizes the recent developments of the
electrocatalyst design for noble metal, non-noble metal, and carbon-based materials.
Introduction - The electrocatalysts facilitate the redox reactions effectively and are classified
as noble-metal based, non-noble metal based, and metal-free carbon-based electrocatalysts.
An ideal electrocatalyst must manifest a low overpotential and rapid kinetics towards HER,
and AOR [5]. The noble metal-based electrocatalysts are pioneers and benchmark
electrocatalysts for both HER and AOR, such as Pt [1], Ir [2], and Ru [3] based compounds.
However, their scarcity limits their widespread usage for large-scale synthesis. OER, and
AOR electrocatalysts without noble metals are therefore encouraged to be investigated under
this strong driving force. The non-noble metal-based electrocatalysts, including the transition
metals, have been developed to enhance hydrogen generation at the cathode and chemical
species oxidation at the anode [4]. Especially, the electrocatalysts were modified
appropriately to optimize the electronic structure, crystal structure, enhance mass transfer,
and charge transport properties to achieve superior performances in the electrocatalytic
processes [6, 7]. The Sabatier principle states that the binding energy between the
electrocatalyst and the reactant should be neither too strong nor too weak. In this way, the
designed electrocatalysts must hold suitable adsorption energies for the reactants to drive the
reaction towards specific products, minimize electrode deactivation, and achieve efficiency
[8], [9]. Accordingly, reduced price-to-performance ratio of the electrocatalyst is highly
favoured to increase the efficiency and viability of hybrid water electrolysis technology. The
efficient price-to-performance ratio suggests the minimum loading of platinum group metals
(PGM) for noble metal based electrocatalysts and development of non-noble metal based and
carbon-based electrocatalysts. Hence, by the above-mentioned strategies, the hybrid water
electrolysis technology advances into the next-gen application of commercialization.
This review summarizes the recent developments of the electrocatalyst design for
noble metal, non-noble metal, and carbon-based materials. Further, the review discusses the
probable anodic reactions for OER and various oxidative products for efficient H 2 production
and generation of value-added products.
The above-mentioned changes have been updated in the revised manuscript. (The
abstract (Page 2, Line 13) , introduction (Page 10, Line 11), section 4 (page 24), and
conclusion (Page 73, Line 11).
Reference:
1. Tran LT, Nguyen QM, Nguyen MD, Le HNT, Nguyen TT, Vu THT. Preparation and
electrocatalytic characteristics of the Pt-based anode catalysts for ethanol oxidation in acid
and alkaline media. International Journal of Hydrogen Energy, 2018. 43(45): p. 20563-
20572.
2. Douk SA, Saravani H. Porous 3D Inorganic Superstructure of Pd–Ir Aerogel as Advanced
Support-Less Anode Electrocatalyst toward Ethanol Oxidation. ACS Omega, 2020. 5(35):
p. 22031-22038.
3. Choi JH, Park Wk, Kwon BK, Sung YE. Methanol Oxidation on Pt/Ru, Pt/Ni, and
Pt/Ru/Ni Anode Electrocatalysts at Different Temperatures for DMFCs. Journal of The
Electrochemical Society, 2003. 150(7): p. A973.
4. Chen Z, Wei W, Song L, Ni BJ. Hybrid Water Electrolysis: A New Sustainable Avenue
for Energy-Saving Hydrogen Production. Sustainable Horizons, 2022. 1: p. 100002.
5. You B, Sun Y. Innovative Strategies for Electrocatalytic Water Splitting. Accounts of
Chemical Research, 2018. 51(7): p. 1571-1580.
6. Jiao J, Yang W, Pan Yuan, Zhang C, Liu S, Chen C, Wang D. Interface Engineering of
Partially Phosphidated Co@Co–P@NPCNTs for Highly Enhanced Electrochemical
Overall Water Splitting. Small, 2020. 16(41): p. 2002124.
7. Barwe S, Mei B, Masa J, Schuhmaqnn W, Ventosa E. Overcoming cathode poisoning
from electrolyte impurities in alkaline electrolysis by means of self-healing electrocatalyst
films. Nano Energy, 2018. 53: p. 763-768.
8. Hideshi O, Jun H, and Kai S. E. The Sabatier Principle in Electrocatalysis: Basics,
Limitations, and Extensions.
9. Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting.
Chemical Society Reviews, 2015. 44(15): p. 5148-5180.
6. Page 9, line 20-25. Why and how the electrocatalysts were modified?
we have provided a detailed explanation.
The electrochemical water splitting is effective and suitable in the first row of transition
metal compounds, such as Fe [1], Co [2], Cu [3], and Ni [4] based materials. The multiple
oxidation states of the transition metal electrocatalysts are responsible for excellent
electrocatalytic AOR and OER activity. The non-noble metal-based electrocatalysts,
including the transition metals, have been developed, such as hydroxides [5], selenides [6],
nitrides [7], phosphides [8], and sulfides [9], which enhance hydrogen generation at the
cathode and chemical species oxidation at the anode [10]. An ideal electrocatalyst must
manifest negligible overpotential and rapid kinetics towards redox reactions [11]. The
multiple oxidation states of the transition metals are responsible for excellent electrocatalytic
AOR and HER activity. Furthermore, the AOR and OER activities highly depend on the
morphology, composition, the electron number of the transition metals, and surface binding
energy of reactants and intermediates. As a result, many prospects for modification of both
physical (conductivity, roughness factor) and chemical (oxidation states) properties of the
material [5]. These modifications can be archived by doping, which increases the
electrochemical active surface area or binary oxide mixture.
The design principle of electrocatalyst involves three aspects, first the intrinsic activity of
electrocatalyst ii) increasing number of active sites, and iii) identifying active reaction
intermediates [12, 13]. Firstly, the intrinsic electrocatalytic activity of the active sites needs to
be improved. By constructing heterojunction structures, bridging active sites with substrates,
heteroatomic doping, creating vacancies, alloying, and adjusting the d-band center and
altering electronic structure of electrocatalyst active sites, the intrinsic activity of the
electrocatalyst can be improved [13]. As a result, the adsorption and desorption energies
between the electrocatalyst and the reactants, intermediates, and products will be optimized,
thereby improving the electrocatalytic reactions. Second, the number of active sites also
affects electrocatalytic performance, especially for multi-electron organic electrooxidation
processes [14]. Therefore, higher surface-to-volume ratio in nanoparticles can expose more
active sites effectively. Meanwhile, the multiple active sites can synergistically improve
electrocatalytic reaction and accelerate its kinetics. A third way to increase electrocatalytic
activity is to identify the active intermediates through advanced in situ characterization and
theoretical studies. in situ electrochemical studies and theoretical modelling of the
electrocatalysts assist in tuning the formation energy of intermediates in the reaction process
and identification of the reaction pathway . [315].
Line 3.
References:
[1] Feng C, Faheem MB, Fu J, Xiao Y, Li C, Li Y. Fe-Based Electrocatalysts for Oxygen
Evolution Reaction: Progress and Perspectives. ACS Catalysis 2020;10(7):4019-47.
[2] Munde AV, Mulik BB, Chavan PP, Sapner VS, Narwade SS, Mali SM, Sathe BR.
Graphene Oxide (Co–Bi@rGO): Reaction Pathway Investigation toward Direct Ethanol Fuel
Cells. The Journal of Physical Chemistry C 2021;125(4):2345-56.
[3] Zhao J, Xue S, Barber J, Zhou Y, Meng J, Ke X. An overview of Cu-based heterogeneous
electrocatalysts for CO2 reduction. Journal of Materials Chemistry A 2020;8(9):4700-34.
[4] Ji X, Zhang Y, Ma Z, Qiu Y. Oxygen Vacancy-rich Ni/NiO@NC Nanosheets with
Schottky Heterointerface for Efficient Urea Oxidation Reaction. ChemSusChem
2020;13(18):5004-14.
Chemistry A 2016;4(45):17587-603.
[6] Cao X, Medvedeva JE, Nath M. Copper Cobalt Selenide as a High-Efficiency
Bifunctional Electrocatalyst for Overall Water Splitting: Combined Experimental and
Theoretical Study. ACS Applied Energy Materials 2020;3(3):3092-103.
[7] Yu L, Zhu Q, Song S, McElhenny B, Wang D, Wu C, Qin Z, Bao J, Yu Y, Chen S, Ren
Z. Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater
electrolysis. Nature Communications 2019;10(1):5106.
[8] Zhang J, Cao X, Guo M, Wang H, Saunders M, Xiang Y, Jiang SP, Lu S. Unique Ni
Crystalline Core/Ni Phosphide Amorphous Shell Heterostructured Electrocatalyst for
Hydrazine Oxidation Reaction of Fuel Cells. ACS Applied Materials & Interfaces
2019;11(21):19048-55.
[9] Zhong M, Li W, Wang C, Lu X. Synthesis of hierarchical nickel sulfide nanotubes for
highly efficient electrocatalytic urea oxidation. Applied Surface Science 2022;575:151708.
[11] You B, Sun Y. Innovative Strategies for Electrocatalytic Water Splitting. Accounts of
Chemical Research 2018;51(7):1571-80.
[12] Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting.
Chemical Society Reviews 2015;44(15):5148-80.

[13] Wang Y, Zou S, Cai W-B. Recent Advances on Electro-Oxidation of Ethanol on Pt- and
Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials. Catalysts2015. p.
1507-34.
[14] Huang J, Jiang Y, An T, Cao M. Increasing the active sites and intrinsic activity of
transition metal chalcogenide electrocatalysts for enhanced water splitting. Journal of
Materials Chemistry A 2020;8(48):25465-98.
[15] Luo J, Vermaas DA, Bi D, Hagfeldt A, Smith WA, Grätzel M. Bipolar Membrane-
Assisted Solar Water Splitting in Optimal pH. Advanced Energy Materials
2016;6(13):1600100.
7. Page 9. Line 47. “anode oxidation reaction” should be revised to “AOR”.
Response: We thank the reviewer for the comment. As per the reviewer’s comment, we have
corrected the anode oxidation reaction in the manuscript to AOR.
Line 17.
8. Page 9, the last paragraph. Please avoid using “We” in the manuscript. Same comment for
the “conclusion” part.
Response: We thank the reviewer for the comment. As per reviewer suggestion we avoided
the using of “We”.
The above-mentioned changes have been updated in the revised manuscript.
Introduction (Page 12, 18), Conclusion (Page 72, Line 11).

9. Page 9. Line 54-59, the sentence should be revised.
we have modified the sentence. The electrochemical anode oxidation of chemical feedstocks
with low theoretical potential is aimed to generate sustainable hydrogen production in the
cathode [1].
11.
Reference:
1. Xu Y, Zhang B. Recent Advances in Electrochemical Hydrogen Production from Water
Assisted by Alternative Oxidation Reactions. ChemElectroChem, 2019. 6(13): p. 3214-
3226.
10. The introduction should be revised to better illustrate the meaning of the review.
comment, we have revised the introduction (Highlighted statements were revised). To date,
concern over environmental safety has led to an upsurge in need to develop alternative green
energy sources to replace the usage of fossil fuels. The hydrogen (H 2) fuel has been identified
as one of the top priorities by energy researchers [1]. Since H2 is clean and cost-effective,
with gravimetric energy density, which in turn proves to be an energy alternative for coming
generations [2, 3]. Currently around 95% of the world’s total hydrogen (H 2) production is
achieved by natural gas, steam reforming or other fossil fuels, which required high
temperature and pressure. The global hydrogen energy requirement has achieved 94 Mt in
2021 which is a 5% increase than in 2020 [4]. Predictions show that in 2030 hydrogen energy
demand would reach 180 Mt that benefits the heavy industry, hydrogen-based fuels and
power generation [5]. Currently, 75 Mt of pure H2 and 45 Mt of mixed gases with H 2 is
produced per year [6]. The global hydrogen market will grow from $142 billion in 2019 to
$209 billion in 2027. However, 95% of the hydrogen produced are from fossil fuels which
result in pollution [7]. The green and sustainable hydrogen generation allows for a low-cost
and highly efficient technology that is crucial for deployment of the hydrogen economy at the
terawatt scale [7]. Otherwise, it is not possible for green hydrogen to compete with grey
hydrogen from fossil fuel (ex. Methane reforming). Electrochemical water splitting as a
promising hydrogen production method attracted great interest in the past decades [1, 2]. The
water electrolysis technology has emerged as an alternative, reliable method for generating
H2 as an efficient and sustainable green energy [8, 9]. Water electrolysis outruns the
performance of most other conventional techniques, which involve two half-reactions,
namely hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) [10].
Conventional water electrolysis methods utilize HER at the cathode and OER at the
anode, which requires higher overpotentials to produce hydrogen. OER follows a sluggish
four-electron transfer pathway which can be ascribed to the dormant kinetics requiring high
potentials to drive the reaction [8]. To tackle these challenges, the hybrid water electrolysis
technology replaces OER at the anode with an alternative anodic oxidation reaction (AOR) of
the chemical substances. In recent years, hybrid water electrolysis systems have rapidly
developed, which offer many advantages over conventional water electrolysis systems as
listed below.
 Electrochemical water splitting for highly efficient hydrogen (H 2) production can be
improved with AOR due to low potential requirement at the anode. By utilizing low-
cost reductive chemical additives, like urea, alcohol, and aldehydes, as sacrificial
agent to substitute for the kinetically sluggish OER, which can greatly lower the cell
voltage input of energy consumption [11].

 In this system, high value-added products, instead of O 2, can be expected to produce
at the anode side of the system by choosing suitable feedstock chemicals and
maximizing the return of energy investment.
 The hybrid water electrolysis system could lower the voltage input and exclude the
formation of H2/O2 gas mixture and reactive oxygen species due to the replacement of
OER with thermodynamically more favorable AOR [12].
In hybrid water electrolysis technology, HER is manifested at the cathode assisted by
the counter oxidative reactions at the anode [13, 14]. The electro-oxidation of various
chemical species has been reported for successful hybrid water electrolysis method, such as
alcohols [15], hydrazine [16], urea [17], ethanol [18], ammonia [19], nitric acid [20], nitrogen
[13], Biomass [21], etc (Scheme 1a). For example, nitric acid is the value-added product with
high monetary value produced from the anodic oxidation of abundant N 2 [13]. Besides,
specific value-added products can be produced by an appropriate choice of oxidative species.
For example, furfural, HMFCA, and furoic acid can be specifically produced by anodic
oxidation of HMF depending on the number of electron transfer process. Similarly, nitric acid
and formic acid are the oxidative reaction products of N 2 and glycerol, respectively. The
application of value-added products produced from hybrid water electrolysis technology
include nitrate which is used to produce fertilizers, gunpowder, and explosives, HMFCA
which is used as furanic polyester interleukin inhibitor and furoic acid used in organic
synthesis of medicines, perfumes, and furoate esters.
The thermodynamical potential requirement for urea electrolysis is comparatively less
than required for OER. Furthermore, urea is globally sufficient in human urine, urea-rich
wastewater, and as a by-product of industrial activities. The two-stage urea oxidation reaction
(UOR) pathway involves the production of intermediate ammonia and the subsequent
decomposition of that ammonia to nitrogen (N2). UOR requires a theoretical potential of

about 0.37 V vs. RHE. As a result, the different rate-determining steps with favorable
thermal/kinetic energetics, the anodic reactions achieve a high current density at
comparatively lower potentials than in conventional OER [17]. The alcohol oxidation
theoretical potential is 0.5 – 1.3 V (vs. SCE). The oxidation of various alcohols (e.g., ethanol,
methanol, and glycerol) are used to substitute OER, and these alcohols were decomposed into
value-added products. The cathode hydrogen production is promoted at a lower potential than
in conventional water electrolysis [13]. The next strategy is nitrogen oxidation reaction
(NOR) which require an equilibrium potential of 1.08 V vs RHE. The electrochemical cells
require only ambient N2 and water as feedstock, making the electrolysis very promising and
cost-effective. The theoretical potential for biomass-derived aldehyde oxidation potential is
in the range <0.5 - >1.0 V vs. RHE. In this platform, biomass-derived chemicals are
particularly appealing because both the organic feeds used and the electricity are renewable,
making the hydrogen (H2) production process sustainable [14, 22, 23]
Scheme 1. (a) Schematic representation of electro-oxidation of various chemical species and
(b) their respective onset potentials in various electrolysis technologies based on previous
reports. The arrow mark represents the onset potential of the reported electrocatalysts in the
RHE scale.
Scheme 1b shows the previously reported electrocatalysts with corresponding onset
potentials for various anode oxidation reactions [2, 13, 18, 20, 24-34]. Despite,
thermodynamically favorable oxidation potential, efficient electrocatalysts are necessary to
drive the electrooxidation process due to sluggish kinetics. Hence, developing highly efficient
electrocatalysts are essential to enhance the activity towards AOR and HER. Several crucial
strategies have been followed to increase the efficiency and commercialization of the hybrid
water electrolysis technology [35], such as electrocatalyst engineering [36] electrolyte
engineering [37], membrane technology [37], and electrolyzer design. Hence, the emerging
field of hybrid water electrolysis system for efficient electrochemical hydrogen production
and generation of value-added products becomes remarkably functional.
The electrocatalysts facilitate the redox reactions effectively and are classified as
noble-metal based [38], non-noble metal based [1], and carbon-based electrocatalysts [39].
The noble metal-based electrocatalysts are pioneers and benchmark electrocatalysts for HER,
OER, and AOR, such as Pt [40], Ir [41], and Ru [42] based compounds. Noble metal based
electrocatalysts exhibit a high exchange current density and lower Tafel slope value due to
the faster electron transfer kinetics between the metal active sites and the electrolytic ions
[43]. However, their scarcity limits their widespread application for large-scale water
electrolyzer. Consequently, noble metals are mostly utilized in different forms of
nanoparticles embedded on conductive supports to take maximum advantage of their defect-
rich surface and increase efficiency at low loading [1]. It is well-known that surface
properties strongly influence the overall electrocatalytic performance of noble metal-based
nanoparticles [1, 3]. OER and AOR electrocatalysts without noble metals are therefore
encouraged to be investigated under this strong driving force.
The electrochemical water splitting is effective and suitable in the first row of
transition metal compounds, such as Fe [44], Co [24], Cu [45], and Ni [46] based materials.
The multiple oxidation states of the transition metal electrocatalysts are responsible for
excellent electrocatalytic AOR and OER activity. The non-noble metal-based
electrocatalysts, including the transition metals, have been developed, such as hydroxides [1],
selenides [47], nitrides [48], phosphides [49], and sulfides [50], which enhance hydrogen
generation at the cathode and chemical species oxidation at the anode [51]. An ideal
electrocatalyst must manifest a negligible overpotential and rapid kinetics towards AOR [52].
The multiple oxidation states of the transition metals are responsible for excellent
electrocatalytic AOR and HER activity. Furthermore, the AOR and OER activities highly
depend on the morphology, composition, the electron transfer number of the transition
metals, and surface binding energy of reactants and intermediates. As a result, many
prospects for modification of both physical (conductivity, roughness factor) and chemical
(oxidation states) properties of the material [1]. These modifications can be archived by
increasing the electrochemical active surface area or binary oxide mixture.
The design principle of electrocatalyst involves three aspects, i) the intrinsic activity
of electrocatalyst ii) increasing number of active sites, and iii) identifying active reaction
intermediates [53, 54]. Firstly, the intrinsic electrocatalytic activity of the active sites needs
to be improved. By constructing heterojunction structures, electronic transfer between active
sites and substrates, heteroatomic doping, creating vacancies, alloying, and adjusting the d-
band center and electronic structure of electrocatalyst active sites [54]. As a result, the
adsorption and desorption energies between the electrocatalyst and the reactants,
intermediates, and products will be optimized, thereby improving the thermodynamic
process. Second, the number of active sites also affects electrocatalytic performance,
especially for multi-electron organic electrooxidation processes [55]. Therefore, higher
surface-to-volume ratio in nanoparticles can expose more active sites effectively. Meanwhile,
the multiple active sites can synergistically improve electrocatalytic reaction and accelerate
its kinetics. A third way to increase electrocatalytic activity is to identify the active
intermediates through advanced in situ characterization and theoretical studies. in situ
electrochemical studies and theoretical modelling of the electrocatalysts assist in tuning the
formation energy of intermediates in the reaction process and identification of the reaction
pathway [52].
In this way, the designed electrocatalysts must hold suitable adsorption energies for
the reactants to drive the reaction towards specific products, minimize electrode deactivation,
and achieve efficiency [56]. Accordingly, reduced price-to-performance ratio of the
electrocatalyst is highly favoured to increase the efficiency and viability of hybrid water
electrolysis technology. The efficient price-to-performance ratio suggests the minimum
loading of platinum group metals (PGM) for noble metal based electrocatalysts and
development of non-noble metal based and carbon-based electrocatalysts [38, 53]. Hence, by
the above-mentioned strategies, the hybrid water electrolysis technology advances into the
next-gen application of commercialization.
The electrochemical hydrogen production by hybrid water electrolysis has recently
attracted interest due to its performance under low overpotentials. Hence, a review addressing
the recent advances in hybrid water electrolysis involving AOR is highly desirable. This
review summarizes the fundamentals of OER and AOR and provide the key parameters for
determining the electrocatalytic activity. Later, the recent developments of the electrocatalyst
design based on noble metal, non-noble metal, and carbon-based materials were discussed.
Further, the review discusses the probable anodic reactions for OER and various oxidative
products for efficient H2 production and generation of value-added products. Oxidative
species including urea, ethanol, methanol, nitrogen, and biomass-derived intermediate
compounds have been discussed in hybrid water electrolysis systems. Finally, the current
challenges and perspectives for technological development for a sustainable hydrogen
economy were included.

The above-mentioned changes have been updated in the revised manuscript Page 5.
References:
Chemistry A 2016;4(45):17587-603.
[2] Hu C, Zhang L, Gong J. Recent progress made in the mechanism comprehension and
design of electrocatalysts for alkaline water splitting. Energy & Environmental Science
2019;12(9):2620-45.
2016;6(13):1600100.
[4] IEA. Hydrogen. 2022 [cited 2023 January 5]; Available from:
https://www.iea.org/reports/hydrogen.
[5] Vesborg PCK, Jaramillo TF. Addressing the terawatt challenge: scalability in the supply
of chemical elements for renewable energy. RSC Advances 2012;2(21):7933-47.
[6] IRENA. Hydrogen. [cited 2023 January 5]; Available from:
https://www.irena.org/Energy-Transition/Technology/Hydrogen.
[7] Chatenet M, Pollet BG, Dekel DR, Dionigi F, Deseure J, Millet P, Braatz RD, Bazant
MZ, Eikerling M, Staffell I, Balcombe P, Shao-Horn Y, Schäfer H. Water electrolysis: from
textbook knowledge to the latest scientific strategies and industrial developments. Chemical
Society Reviews 2022;51(11):4583-762.
[8] Zhang H, Maijenburg AW, Li X, Schweizer SL, Wehrspohn RB. Bifunctional
Heterostructured Transition Metal Phosphides for Efficient Electrochemical Water Splitting.
Advanced Functional Materials 2020;30(34):2003261.

[9] Artero V, Chavarot-Kerlidou M, Fontecave M. Splitting Water with Cobalt. Angewandte
Chemie International Edition 2011;50(32):7238-66.
[10] Surendran S, Shanmugapriya S, Sivanantham A, Shanmugam S, Kalai Selvan R.
Electrospun Carbon Nanofibers Encapsulated with NiCoP: A Multifunctional Electrode for
Supercapattery and Oxygen Reduction, Oxygen Evolution, and Hydrogen Evolution
Reactions. Advanced Energy Materials 2018;8(20):1800555.
[11] Li Y, Wei X, Han S, Chen L, Shi J. MnO2 Electrocatalysts Coordinating Alcohol
Oxidation for Ultra-Durable Hydrogen and Chemical Productions in Acidic Solutions.
Angewandte Chemie International Edition 2021;60(39):21464-72.
2020;11(1):4594.
[13] Kuang M, Wang Y, Fang W, Tan H, Chen M, Yao J, Liu C, Xu J, Zhou K, Yan Q.
Efficient Nitrate Synthesis via Ambient Nitrogen Oxidation with Ru-Doped TiO2/RuO2
Electrocatalysts. Advanced Materials 2020;32(26):2002189.
[14] Chadderdon XH, Chadderdon DJ, Pfennig T, Shanks BH, Li W. Paired electrocatalytic
hydrogenation and oxidation of 5-(hydroxymethyl)furfural for efficient production of
biomass-derived monomers. Green Chemistry 2019;21(22):6210-9.
[15] Bai J, Liu D, Yang J, Chen Y. Nanocatalysts for Electrocatalytic Oxidation of Ethanol .
ChemSusChem 2019;12(10):2117-32.
[16] Sun Q, Wang L, Shen Y, Zhou M, Ma Y, Wang Z, Zhao C. Bifunctional Copper-Doped
Nickel Catalysts Enable Energy-Efficient Hydrogen Production via Hydrazine Oxidation and
Hydrogen Evolution Reduction. ACS Sustainable Chemistry & Engineering
2018;6(10):12746-54.
[17] Patil SJ, Chodankar NR, Hwang S-K, Rama Raju GS, Huh Y-S, Han Y-K. Fluorine
Engineered Self-Supported Ultrathin 2D Nickel Hydroxide Nanosheets as Highly Robust and
Stable Bifunctional Electrocatalysts for Oxygen Evolution and Urea Oxidation Reactions.
Small 2022;18(7):2103326.
[18] Qiu Y, Zhang J, Jin J, Sun J, Tang H, Chen Q, Zhang Z, Sun W, Meng G, Xu Q, Zhu Y,
Han A, Gu L, Wang D, Li Y. Construction of Pd-Zn dual sites to enhance the performance
for ethanol electro-oxidation reaction. Nature Communications 2021;12(1):5273.
[19] Zott MD, Garrido-Barros P, Peters JC. Electrocatalytic Ammonia Oxidation Mediated
by a Polypyridyl Iron Catalyst. ACS Catalysis 2019;9(11):10101-8.
[20] Wang D, He N, Xiao L, Dong F, Chen W, Zhou Y, Chen C, Wang S. Coupling
Electrocatalytic Nitric Oxide Oxidation over Carbon Cloth with Hydrogen Evolution
Reaction for Nitrate Synthesis. Angewandte Chemie International Edition
2021;60(46):24605-11.
[21] Gouda L, Sévery L, Moehl T, Mas-Marzá E, Adams P, Fabregat-Santiago F, Tilley SD.
Tuning the selectivity of biomass oxidation over oxygen evolution on NiO–OH electrodes.
Green Chemistry 2021;23(20):8061-8.
[22] Sun H, Kim H, Song S, Jung W. Copper foam-derived electrodes as efficient
electrocatalysts for conventional and hybrid water electrolysis. Materials Reports: Energy
2022;2(2):100092.
[23] Munde AV, Mulik BB, Chavan PP, Sapner VS, Narwade SS, Mali SM, Sathe BR.
Graphene Oxide (Co–Bi@rGO): Reaction Pathway Investigation toward Direct Ethanol Fuel
Cells. The Journal of Physical Chemistry C 2021;125(4):2345-56.

[24] Meng X, Ouyang Y, Wu H, Huang H, Wang F, Wang S, Jiang M, Zhang LY.
Hierarchical defective palladium-silver alloy nanosheets for ethanol electrooxidation. Journal
of Colloid and Interface Science 2021;586:200-7.
[25] Rodríguez-Gómez A, Lepre E, Sánchez-Silva L, López-Salas N, de la Osa AR. PtRu
nanoparticles supported on noble carbons for ethanol electrooxidation. Journal of Energy
Chemistry 2022;66:168-80.
[26] Chen H-S, Benedetti TM, Lian J, Cheong S, O’Mara PB, Sulaiman KO, Kelly CHW,
Scott RWJ, Gooding JJ, Tilley RD. Role of the Secondary Metal in Ordered and Disordered
Pt–M Intermetallic Nanoparticles: An Example of Pt3Sn Nanocubes for the Electrocatalytic
Methanol Oxidation. ACS Catalysis 2021;11(4):2235-43.
[27] Tong Y, Yan X, Liang J, Dou SX. Metal-Based Electrocatalysts for Methanol Electro-
Oxidation: Progress, Opportunities, and Challenges. Small 2021;17(9):1904126.
[28] Jiang Y-C, Sun H-Y, Li Y-N, He J-W, Xue Q, Tian X, Li F-m, Yin S-B, Li D-S, Chen
Y. Bifunctional Pd@RhPd Core–Shell Nanodendrites for Methanol Electrolysis. ACS
Applied Materials & Interfaces 2021;13(30):35767-76.
[29] Yaqoob L, Noor T, Iqbal N, Nasir H, Mumtaz A. Electrocatalytic performance of
NiNH2BDC MOF based composites with rGO for methanol oxidation reaction. Scientific
Reports 2021;11(1):13402.
[30] Dai C, Sun Y, Chen G, Fisher AC, Xu ZJ. Electrochemical Oxidation of Nitrogen
towards Direct Nitrate Production on Spinel Oxides. Angewandte Chemie International
Edition 2020;59(24):9418-22.
[31] Liu Q, Li M-Y, Shi Y-M, Liu C-B, Yu Y-F, Zhang B. In situ structural reconstruction of
NiMo alloy as a versatile organic oxidation electrode for boosting hydrogen production. Rare
Metals 2022;41(3):836-43.
[32] Li Y, Ding J, Liu X, Wang J, Jiao S, Kang N, Li J, Irfan M, Zhang P. Physically mixed
Ni2Co/graphene catalyst for enhanced glucose oxidation in a glucose fuel cell. Biomass
Conversion and Biorefinery 2022.
[33] Huang S, Li J, Chen Y, Yan L, Zhang P, Zhang X, Zhao C. Boosting the anti-poisoning
ability of palladium towards electrocatalytic formic acid oxidation via polyphosphide
chemistry. Journal of Colloid and Interface Science 2022;615:366-74.
[34] Barwe S, Mei B, Masa J, Schuhmann W, Ventosa E. Overcoming cathode poisoning
from electrolyte impurities in alkaline electrolysis by means of self-healing electrocatalyst
films. Nano Energy 2018;53:763-8.
[35] Deng C, Toe CY, Li X, Tan J, Yang H, Hu Q, He C. Earth-Abundant Metal-Based
Electrocatalysts Promoted Anodic Reaction in Hybrid Water Electrolysis for Efficient
Hydrogen Production: Recent Progress and Perspectives. Advanced Energy Materials
2022;12(25):2201047.
[36] Griffiths RJ, Burley GA, Talbot EPA. Transition-Metal-Free Amine Oxidation: A
Chemoselective Strategy for the Late-Stage Formation of Lactams. Organic Letters
2017;19(4):870-3.
[37] Xu Y, Zhang B. Recent Advances in Electrochemical Hydrogen Production from Water
Assisted by Alternative Oxidation Reactions. ChemElectroChem 2019;6(13):3214-26.
[38] Fu X, Wan C, Huang Y, Duan X. Noble Metal Based Electrocatalysts for Alcohol
Oxidation Reactions in Alkaline Media. Advanced Functional Materials
2022;32(11):2106401.
[39] Younis MA, Hou Y. Chapter 10 - Nanocarbon-Based Hybrids as Electrocatalysts for
Hydrogen and Oxygen Evolution From Water Splitting. In: Zhao Q, editor. Advanced
Nanomaterials for Pollutant Sensing and Environmental Catalysis: Elsevier; 2020. p. 379-
418.
[40] Tran LT, Nguyen QM, Nguyen MD, Thi Le HN, Nguyen TT, Thi Vu TH. Preparation
and electrocatalytic characteristics of the Pt-based anode catalysts for ethanol oxidation in
acid and alkaline media. International Journal of Hydrogen Energy 2018;43(45):20563-72.
[41] Shafaei Douk A, Saravani H. Porous 3D Inorganic Superstructure of Pd–Ir Aerogel as
Advanced Support-Less Anode Electrocatalyst toward Ethanol Oxidation. ACS Omega
2020;5(35):22031-8.
[42] Choi J-H, Park K-W, Kwon B-K, Sung Y-E. Methanol Oxidation on Pt/Ru, Pt/Ni, and
Electrochemical Society 2003;150(7):A973.
[43] Phan QT, Poon KC, Sato H. A review on amorphous noble-metal-based electrocatalysts
for fuel cells: Synthesis, characterization, performance, and future perspective. International
Journal of Hydrogen Energy 2021;46(27):14190-211.
[44] Feng C, Faheem MB, Fu J, Xiao Y, Li C, Li Y. Fe-Based Electrocatalysts for Oxygen
Evolution Reaction: Progress and Perspectives. ACS Catalysis 2020;10(7):4019-47.
[45] Zhao J, Xue S, Barber J, Zhou Y, Meng J, Ke X. An overview of Cu-based
heterogeneous electrocatalysts for CO2 reduction. Journal of Materials Chemistry A
2020;8(9):4700-34.
[46] Ji X, Zhang Y, Ma Z, Qiu Y. Oxygen Vacancy-rich Ni/NiO@NC Nanosheets with
Schottky Heterointerface for Efficient Urea Oxidation Reaction. ChemSusChem
2020;13(18):5004-14.
[47] Cao X, Medvedeva JE, Nath M. Copper Cobalt Selenide as a High-Efficiency
Bifunctional Electrocatalyst for Overall Water Splitting: Combined Experimental and
Theoretical Study. ACS Applied Energy Materials 2020;3(3):3092-103.

[48] Yu L, Zhu Q, Song S, McElhenny B, Wang D, Wu C, Qin Z, Bao J, Yu Y, Chen S, Ren
Z. Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater
electrolysis. Nature Communications 2019;10(1):5106.
[49] Zhang J, Cao X, Guo M, Wang H, Saunders M, Xiang Y, Jiang SP, Lu S. Unique Ni
Crystalline Core/Ni Phosphide Amorphous Shell Heterostructured Electrocatalyst for
Hydrazine Oxidation Reaction of Fuel Cells. ACS Applied Materials & Interfaces
2019;11(21):19048-55.
[50] Zhong M, Li W, Wang C, Lu X. Synthesis of hierarchical nickel sulfide nanotubes for
highly efficient electrocatalytic urea oxidation. Applied Surface Science 2022;575:151708.
[52] You B, Sun Y. Innovative Strategies for Electrocatalytic Water Splitting. Accounts of
Chemical Research 2018;51(7):1571-80.
[53] Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting.
Chemical Society Reviews 2015;44(15):5148-80.
The above-mentioned changes have been updated in the revised manuscript .
11. Section 2. As the review was about the hydrogen evolution, the mechanism of hydrogen
evolution in the cathode is recommended to be added in this section. -
suggestion, we have included the HER mechanism.
Mechanism of HER
Hydrogen evolution reaction (HER) is composed of two-step electron transfer process
that takes place on the cathode, forming hydrogen (H 2) [1]. Initially, during HER, the protons
are adsorbed (H*) on the active sites (M) of electrode by water (H 2O) dissociation with one
electron transfer from the electrode surface, which is called the Volmer step (Eqn 1).
Subsequently, there are two possible pathways to form hydrogen (H 2). First one is the
combination of adsorbed proton (H*) with one electron transferred from the electrode and
one proton from the electrolyte, resulting in one hydrogen (H 2) molecule, which is the
Heyrovsky step (Eqn 2). The other step is a faster reaction pathway named the Tafel step
(Eqn 3), which involves the direct formation of a H 2 molecule from two adsorbed protons
(H*) from the surface of electrocatalyst. [2]
In alkaline media
Volmer step: M + H2O + e- → M* + OH- (1)
Heyrovsky step: H2O + M-H* + e- → H2 + OH- (2)
Tafel step: 2M-H* → 2M + H2 (3)
9.
References:
[1] Zhang H, Maijenburg AW, Li X, Schweizer SL, Wehrspohn RB. Bifunctional
Heterostructured Transition Metal Phosphides for Efficient Electrochemical Water Splitting.
Advanced Functional Materials 2020;30(34):2003261.
[2] Zhao G, Rui K, Dou SX, Sun W. Heterostructures for Electrochemical Hydrogen
Evolution Reaction: A Review. Advanced Functional Materials 2018;28(43):1803291.

12. Fig. 1B, legend should be given in show the meaning of ΔG, E0, E1, E2, E3 and Ƞshould
be given.
comment, we have given the meaning of ΔG, E0, E1, E2, E3 and Ƞ (Fig. R4b) in the revised
manuscript. The reaction energy of each elementary step and the OER scaling relationship
between the real and ideal electrocatalyst reveal the binding energy of the metal surface for
the adsorbed hydroxide ions as shown in Fig. R4b. ΔG represents the free energy of
formation for the reaction intermediates which is exothermic/energy releasing when negative
and endothermic/energy consuming when positive. E 0 denotes the standard reversible
electrode potential of the HER, and the E 1, E2, E3 represent the different electrode potentials,
and Ƞ is the overpotential. The energetics of real and ideal catalyst at various electrode
potentials are better illustrated. At the electrode potential E 1, for either catalyst, all steps are
uphill, so OER cannot proceed. ΔG for the reaction intermediates determines the potential
determining step in most electrochemical conversion reactions. Hence, for OER, Eqn. R1
describes potential limiting step for OER which ascribes the required high potential of 1.23 V
to drive the electrocatalytic reactions.
Fig. R41. (a) Schematic representation of OER mechanism in the alkaline condition. (Blue
line indicates the M-OOH pathway, whereas the purple line indicates the direct reaction of
two (M-O) species to evolve oxygen. (b) The plot of Gibbs free energy reaction pathways of
the intermediates of a real and ideal electrocatalyst for the OER mechanism.
If the kinetic limitations are negligible, the ideal catalyst has no overpotential at the
reversible electrode potential. To make all steps downhill for the real electrocatalyst, E 3 is
required, at which OER can occur at a prescribed pace [1]. As a result of irregular variations
in the adsorption energies of the intermediate species, the binding energies for each step are
different. The strong binding energy of O 2 will increase the complication of MOOH
formation, and the weak binding energy of oxygen to the surface can increase the difficulty of
MO formation [58].
M-OOH + OH¯ → M + O2(g) + H2O + e¯ (R1)
9.
Reference:
1. Holger D, Christian L, Tobias R, Marcel R, Stefan R and Peter S. The Mechanism of
Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis,
ChemCatChem 2010,2,724-761.
[13.] Page 12, line 15-21. Any other fuels except hydrogen? References should given here.
in hybrid water electrolysis, hydrogen is produced at the cathode assisted by the counter
anodic reactions with chemical species at the anode. The hybrid water electrolysis is
considered an efficient method for hydrogen (H 2) production and simultaneous conversion of
anodic substances to desired products [1]. The biomass-derived products like HMF, furfural,
and glucose into specific value-added products in alkaline media. The common oxidation of
furan compounds are often important chemical feedstocks in various polymer and
pharmaceutical industries [2-4]. The application of value-added products produced from
hybrid water electrolysis technology include nitrate which is used to produce fertilizers,
gunpowder, and explosives, HMFCA which is used as furanic polyester interleukin inhibitor
and furoic acid used in organic synthesis of medicines, perfumes, and furoate esters.
The above-mentioned changes have been updated in the revised manuscript Page 8, 15.
References:
1. Zhijie C, Wei W, Lan S, Bing-J N. Hybrid Water Electrolysis: A new Sustainable Avenue
for Energy-Saving Hydrogen Production. Sustainable Harizons 1 (2022) 100002.
[2.] Jiao Y, Misuk C, Younghwan L. Synthesis of hierarchical NiCOo2O4 hollow nanorods
via sacrificial-template accelerate hydrolysis for electrochemical glucose oxidation.
Biosensors and Bioelectronics 75 (2016) 15-22.
2.[3.] Dr.Chen D, Dr. Kuang H W, Xinxin L, Dr. Soshan C, Richard D, Tilley, et al. Ligand-
Promoted Cooperative Electrochemical Oxidation of Bio-Alcohol on Distorted Cobalt
Hydroxides for Bio-Hydrogen Extraction. ChemSusChem 2021, 14, 1-10.
3.[4.] Chen D, Cui Y T, Xuan LI, Jingjin T, Hengpan Y, Qi HU, Chuanxin H. Earth-
Abundant Metal-Based Electtrocatalyst Promoted Anodic Reaction in Hybrid Water

Electrolysis for Efficient Hydrogen Production: Recent Progress and Perspectives. Adv.
Energy Materials 12, 25, 7(2022) 2201047.
13.[14.] Fig.2. References of the values in the figure should be given.
the polarization curve of OER [1], AOR [2, 3], and HER [3] can be seen to indicate that OER
requires higher overpotentials to reach the same current density as AOR. We attached the
reference for Fig.2R1 with theoretical potential values.
Fig. 2R1. The comparison of various anode reaction potentials in the water electrolysis
system.
The above-mentioned changes have been updated in the revised manuscript
Page 19.
References:
1. Xiaoxin Z and Yu Z. Noble metal – free hydrogen evolution catalysts for water splitting.
Chem. Soc. Rev., 2015, 44,5148.
2. Yingjie S, Kaiyue J, Haohong D, Mingfei S. Hydrogen production coupled with water and
organic oxidation based on layered double hydroxides. Exploration 2021, 1, 20210050.

3. Tehua W, Li T, Xiaorong Z, Chen C, Wei C, Shiqian D, et al. Combined anodic and
Nature Catalysis 5, 66-73 (2022).
14.[15.] Section 3.2.” Tafel plot” is a kind of measurement but not parameter.
Response: We thank the reviewer comment. As per the reviewer’s comment, Tafel plot is the
tool to quantify the degree of reaction kinetics in an electrocatalytic process. Tafel plot (log j
vs. overpotential (mV)) is a measure of electrochemical kinetics relating the rate of an
electrochemical reaction to the overpotential. The slope of the Tafel plots explains the
required potential to drive a decade of reactions, where the unit is mV dec -1. The faster the
reaction kinetics, lower is the Tafel slope and vice versa. Hence, a lower Tafel slope value is
preferred in an electrochemical reaction which is an important parameter of an efficient
electrocatalyst. [1].
The above-mentioned changes have been updated in the revised manuscript Page
20 Line 17.
Reference:
[1] Shinagawa T, Garcia-Esparza AT, Takanabe K. Insight on Tafel slopes from a
microkinetic analysis of aqueous electrocatalysis for energy conversion. Scientific Reports
2015;5(1):13801.
15.[16.] Section 4.1. The first paragraph. Definition of noble metal based electrocatalyst
should be given first at the beginning of the paragraph. Why noble metal- based
electrocatalysts were with high exchange current density and low Tafel slope value?
comment, we have included the definition of noble metal based electrocatalyst at the
beginning of the paragraph. The noble metal-based electrocatalysts are pioneers and
benchmark electrocatalysts for both HER, OER, and AOR, such as Pt[1], Ir [2], and Ru [3]
based compounds. Noble metal based electrocatalysts exhibit a high exchange current density
and lower Tafel slope value due to the faster electron transfer kinetics between the metal
active sites and the electrolytic ions [4]. However, their scarcity limits their widespread
application for large-scale water electrolyzer. Consequently, noble metals are mostly utilized
in different forms of nanoparticles embedded on conductive supports to take maximum
advantage of their defect-rich surface and increase efficiency at low loading [5]. It is well-
known that surface properties strongly influence the overall electrocatalytic performance of
noble metal-based nanoparticles [5, 6]. OER and AOR electrocatalysts without noble metals
are therefore encouraged to be investigated under this strong driving force. Hence, the higher
electron transfer between the noble metal active centers and the analyte, elucidates a faster
reaction kinetics resulting in high exchange current density and lower Tafel slope value for
noble metal based electrocatalysts compared to other electrocatalytic elements.
5.
References:
[1] Tran LT, Nguyen QM, Nguyen MD, Thi Le HN, Nguyen TT, Thi Vu TH. Preparation and
electrocatalytic characteristics of the Pt-based anode catalysts for ethanol oxidation in acid
and alkaline media. International Journal of Hydrogen Energy 2018;43(45):20563-72.
[2] Shafaei Douk A, Saravani H. Porous 3D Inorganic Superstructure of Pd–Ir Aerogel as
Advanced Support-Less Anode Electrocatalyst toward Ethanol Oxidation. ACS Omega
2020;5(35):22031-8.
[3] Choi J-H, Park K-W, Kwon B-K, Sung Y-E. Methanol Oxidation on Pt/Ru, Pt/Ni, and
Electrochemical Society 2003;150(7):A973.
[4] Phan QT, Poon KC, Sato H. A review on amorphous noble-metal-based electrocatalysts
for fuel cells: Synthesis, characterization, performance, and future perspective. International
Journal of Hydrogen Energy 2021;46(27):14190-211.
Chemistry A 2016;4(45):17587-603.
2016;6(13):1600100.
16.[17.] A table summarizing and comparing the different electrocatalysts is recommended to
be added in section 4.
suggestion we have summarized and compared the different electrocatalysts in a table.
Specific
Oxidation ECSA Onset
Electrocatalyst Electrolyte activity (SA) Ref.
Species [m2g-1] potential (V)
[mA cm-2]
Methanol Pt/Ni(OH)2/graphene 1M KOH + 64.1 0.40 V 1.93 1

1M MeOH
Methanol PtAuRu/rGO 1M KOH + - 0.42 V - 2
1M MeOH
Methanol PtCu nano 0.5 M KOH + 12.4 0.41 V 18.2 3
1 M MeOH
framework
Methanol Pt1Ni1/C 1M KOH + 1 29.8 0.42 V 11.5 4

M MeOH
Methanol Rh3Co 1M KOH + 51.7 0.22V 0.593 5
1M MeOH
Ethanol SANi-Pt NWs 1M KOH + 106.2 0.30 V 5.27±0.34 6
1M EtOH
±4.5
Ethanol PtMo/C 0.5 M KOH + 31.6 0.31 V 3.17 7

0.5 M EtOH
Ethanol Pd Aerogel 0.5 M KOH + 56.1 0.32 V 6.59 8
1 M EtOH
Ethanol RhPb-PbO2/C 1 M KOH + 1 - 0.28 V - 9
M EtOH
Ethanol Rh CPT 1 M KOH + 1 51.3 0.13 V 0.361 10
M EtOH
nanobranches
Urea Cr-Ni(OH)2 1 M KOH + - 0.15 V - 11

0.33 M Urea
Urea Ni-CuO NAs/CF 1 M KOH + 15.0 0.08 V - 12
0.33 M Urea
HMF CoCu- Bimetallic 1 M KOH + - 0.17 V - 13
50 mM HMF
Nitrogen RuMn3O4 N2 saturated - 0.37 V - 14
0.1 M
Na2SO4
References:
1. Wenjing H, Honggtao, Jigang Z, Paul N D, David M, Peng Z, et al. Highly active and
durable methanol oxidation electrocatalysts based on the synergy platinum nickel
hydroxide-graphene. Nature communication 6, 10035 (2015).
2. Fangfang R, Caiqin W, Chunyang Z, fengxing J, Ruirui Y, Yukou D, Pong Y and Jingkun
X. One-pot synthesis of a rGO-supported ultrafine ternary PtAuRu catalyst with high
electrocatalytic activity towards methanol oxidation alkaline medium. J. Mater.Chem. A,
2013,1,7255-7261.
3. Zhicheng Z, Zhimin L, Chao W, Jian Z, Junze C, Xiao Z, et al. One-Pot Synthesis of
Highly Anistropic Five-Fold-Twinned PtCu Nanoframes Used as a Bifunctional
Electrocatalyst for Oxygen Reduction and Methanol Oxidation. 28,39, (2016), 8712-8717.
4. Siqi L, Huiming L, Jingyao S, zhongbin Z. Promoting the methanol oxidation catalytic
activity by introducing surface nickel on platinum nanoparticles. Nano Research 11, 2058-
2068 (2018).
5. Ya-Nan Z, Ying L, Jing-Y Z, Yu-C J, Shu-N l, Yu C. The electrocatalytic performance of
carbon ball supported RhCo alloy nanocrystals for the methanol oxidation reaction in
alkaline media. Journal of Power Sources, 371,15, (2015), 129-135.
6. Mufan L, Kaining D, Chengzhang W, Tao C, Liang Z, Sheng D, Wenxin C, Zipeng Z, et
al. Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional
electrocatalysis. Nature Catalysis 2, 495-503 (2019).
7. W.J. Pech-R, D.Gonzalez-Q, G. Vargas-G, C.Morais, T.W.Napporon, F.J. Rodriguez-
Varela, Apply cat.B: Environmental 203,2017, 654-662.
8. Mehdi Z Y-A, Meissam Nr, Ali Reza M A, and hamideh S. Palladium aerogel as ahigh-
performance electrocatalyst for ethanol electro-oxidation in alakaline media. J.
Mater.Chem.A, 2017,5, 10244-10249.
9. Bing L, Min H, Rui-L W, Chao-N W, Qiong-L W, Yao-Y Y. Ethanol Electrooxidation on
Rhodium-Lead Catalysts in Alkaline Media: High Mass Activity, Long-Term Durability,
and Considerable Co2 Selectivity. Small 2020, 2004380.
10. Jiawei Z, Jinyu Y, Quiyuan F, Yating J, Yifan Z, Huiqi L. Cyclic Pen-Twinned Rhodium
Nanobranches as Superior Catalysts for Ethanol Electro-oxidation. J.Am. Chem.Soc.
2018,140,36,11232-11240.
11. Jichao Z, Xuedan S, Liqun K, Jiexin Z, Longxiang L, Qing Z, Dan J.L.B, et al. Stabilizing
efficient structures of superwetting electrocatalysts for enhanced urea oxidation reactions.
Chem Catalysis, 2, 11, 2022, 3254-3270.
12. Hainan S, Jiapeng L, Hyunseung K, Sanzhao S, Liangshuang F, Zhiwei H. et al. Ni-Doped
CuO Nanoarrays Activate Urea Adsorption and Stabilizes Reaction Intermediates to
Achieve High-performance Urea Oxidation Catalysts. Avanced Science, 9,34,2022,
2204800.
13. Yanwei Z, Jianqiao S, Yingying L, Yuxuan L, Bo Z, Shuangyin W, Yuquin Z.
Understanding the surface segregation behavior of bimetallic CoCu Toward HMF
oxidation reaction. J. Jechem 74, 2022, 85-90.
14. Zhongfen N, Linlin Z, Xin D, Meiyu C, Fanfan X, Lehui M, Mingxia G, Mingzhu L,
Lixue Z. Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation
by Ru-Nanoclusters-Coupled Mn3O4 Catalysts Decorated with Atomically Dispersed Ru
Atoms. Adv. Materials, 34,14,2022,2108180.
17.[18.] Page 20. Line 1 Reference should be given.
Response: We thank the reviewer for the valuable comment. As per reviewer comment we
corrected the revised manuscript. The turnover frequency of Rh/RhOx reached 2.19 S -1 at
1.53 V and 20.30 s-1 at 1.63 V, which are 72.0 times and 42.2 times higher than Rh. The
electrocatalyst displays promising stability of more than 20 hours at 50 mA cm-2 [1].
Line 18.
Reference:
1. Liu S, Ji Y, Yang S, Li L, Shao Q, Hu Z, et al. Spontaneous amorphous oxide-interfaced
ultrafine noble metal nanoclusters for unexpected anodic electrocatalysis. Chem Catalysis,
2021. 1(5): p. 1104-1117.
18.[19.] Section 4.3. The statement should be consistent through out the manuscript.
corrected the statement for carbanions based electrocatalyst to carbon based electrocatalyst.
The above-mentioned changes have been updated in the revised manuscript
19.[20.] Section 4. Are there any strategies to upgrade the electrocatalysts? A brief review of
the strategies would be very helpful for readers to better acknowledge the development of
electrocatalysts.
we have mentioned the electrocatalyst design strategies for the better performance of hybrid
water electrolyzer in the revised manuscript as given below:
Electrocatalyst design strategy
The electrocatalyst design strategies are explained in the following categories:
anion/cation regulation, surface engineering, interface engineering, and carbon incorporation.
1.1 Anion/cation regulation
In order to increase the free carrier density and active sites of electrocatalysts, anion
regulation has been considered as a promising method for modifying electrocatalytic activity.
The anions, like B, P, S, Se, O, N, Te, etc., based materials have a high degree of flexibility
in modulating local electronic structures and surface adsorption properties, making them a
promising candidate for the development of advanced electrocatalysts with improved
performance and lower noble metal loadings [1]. A critical role of anions is first
demonstrated by their strong electronegativity, which allows them to attract electrons from
metal atoms and then work with metal active sites to capture positively charged protons,
improving catalytic performance. By introducing anions, metal atoms would be distanced
from each other, and their interactions would be weakened. In addition to lattice expansion,
tensile strain is also an important factor that affects electronic properties [1, 2].
In addition to anion modulation, metal cation doping has also been investigated to explore
high-performance electrocatalysts. The fabrication of cation doping as highly active
electrocatalysts requires careful control of their composition, size, and shape during
nucleation and growth. The different atomic sizes, electronegativity, and unique physical and
chemical properties of the doped cations significantly influence the electrocatalytic activity
[3]. However, this kinetic process remains poorly understood, and it is consequently difficult
to simultaneously tune all the structural parameters of the obtained catalysts. After cation
exchange reactions, active facets with high surface energy can serve as electrocatalytic active
sites for HER, OER, and AOR [4].
1.2 Surface engineering
The surface engineering strategies are widely used to enhance electrocatalytic activity. A
rational design of electrocatalyst surfaces enhances the electrical conductivities, increases the
number of active sites, and is efficient in optimizing intermediate adsorption/desorption
characteristics [5]. The surface engineering approaches are divided into three categories,
including defect and vacant engineering, surface morphology engineering, and
crystallographic tailoring. The defect engineering involves the introduction of heteroatom,
edge sites, and vacancy. The surface morphology engineering utilizes one-dimensional (1D),
two-dimensional (2D) and three-dimensional (3D) nanostructure arrays to control the electron
transfer pathways, active sites exposure, and surface unique surface energy which greatly
benefits HER, OER and AOR [6]. The crystallographic tailoring includes the control of faces
in crystals as well as modifying surface phases [7].
1.2.1 Defect and vacancy engineering
Generally, nanomaterials can be engineered with lattice defects, interstitial atoms, and
vacancies in their defect structures. Defect is a desired surface property of electrocatalysts,
which can modify electronic structures and provide additional active sites for electrocatalysts
[5]. Thereby surface defects affects catalytic activity and can change charge distribution and
adsorption/desorption behavior of reactants and products [7, 8]. Due to lattice defects,
transition metal dichalcogenides have abundant electrocatalytic edge sites which contribute to
improved electrocatalytic activity. In addition, topological defects in nanocarbon may be able
to tailor the electrocatalytic performances by introducing heteroatom dopants with varied size
and electronegativity [9, 10]. Therefore, electrocatalysts containing transition metal elements,
oxygen and sulfur with defects and vacancies can modulate their electronic configuration,
making them more efficient.
1.2.2 Surface morphology engineering
Materials with 1D , 2D and 3D nanostructures have been explored and developed due to
the size of electrocatalysts, where this morphology can enhance the number of active sites
and mass transfer [11]. Surface engineering strategy has been a crucial method to increase the
electrocatalytic activity by designing 1D, 2D and 3D nanostructures [11, 12]. In general, 1D
nanostructures consist of nanowires, nanobelts, nanorods, nanofibers, nanotubes, etc. A 1D
nanostructure’s unique physicochemical properties make it very attractive for
electrocatalysis. As a result of this, electron transport can be significantly enhanced through

the direct transfer pathway. There has been a great deal of effort expended in investigating
2D nanostructure materials as efficient electrocatalysts for the catalyst field, similar to the
active material with 1D nanostructures [13]. Nanosheets, nanoflakes, nanowalls, nanofilms,
and nanoplates are examples of 2D nanostructures. In addition to their large specific surface
area, 3D nanostructures usually have fast mass-charge transport channels and enriched active
sites, making them excellent electrocatalysts [14]. A smaller crystal size increases the
efficiency of the active material if it is well dispersed, thus improving catalytic activity. As a
result, the catalyst must be limited in size to ensure reactivity and avoid aggregation.
1.2.3 Crystallographic tailoring
The surface property of crystals, such as the surface phase and the surface facet, can
have a significant influence on active site reactivity [15]. The electrocatalytic performance of
electrocatalysts can be significantly improved by designing and controlling exposure to
specific facets. As a result of the different crystal facets [16], different coordinated atoms and
different surface energies determines the electrocatalytic kinetics. The electrocatalytic
activity of highly active crystal facets can therefore be significantly enhanced by the selective
exposure to the reactants [17].
1.3 Interface engineering
Researchers have been focused on nanointerfaces among heterointerface and hybrid
compounds to develop synergetic effects between different elements to tailor the electronic
structure of electrocatalysts [15]. Consequently, modulated electronic structure influences the
overall performance of electrocatalysts. In recent years, self-supported electrocatalysts are
under the vigorous research due to their highly favorable interfaces for the desired
electrocatalytic activity [12]. During the overall charge transport in a self-supported
electrocatalyst, three interfacial processes are involved: 1. Inner electrocatalyst, 2. Substrate/

catalyst interface, 3. Electrolyte/ catalyst interface. The control of these interfaces is
important for improving the performance of self-supported electrocatalysts. [12].
1.3.1 Heterostructure design
The unique physicochemical properties of heterostructure electrocatalysts make them
excellent electrocatalysts for electrochemical water electrolysis. The combined different
components will create synergistic effects, strong electronic interactions, or support effects at
interfaces, resulting in greater electrocatalytic activity than the individual components.
Therefore, developing advanced electrocatalysts with well-defined interfaces requires the
construction of heterostructures. The synergistic effects, electronic interaction, and support
effects of the heterostructure electrocatalysts prove to be a promising strategy for efficient
hybrid water electrolysis performances [18]. The combined activity of different phases in a
heterostructure electrocatalyst yield multiplied performances of the individual phases.
Besides, the change in electronic structure across the hetero interfaces enables tunable
adsorption desorption free energies for the reactants. Additionally, the significant effect of the
support plays a crucial role in increasing electrocatalytic activity, including improved
conductivity, exposed active sites, stability, and mass transport [19, 20]. Hence, the
heterostructure properties collectively promote higher performances for hybrid water
electrolysis.
1.3.2 Electrolyte/ Electrocatalyst interface
The modified electrocatalyst/ electrolyte interface is effective to increase the
performance of AOR and HER in hybrid water electrolyzer [21]. By controlling the
aerophilic/ anaerobic or hydrophilic/ hydrophobic properties of electrocatalyst, the mass
transport among the electrolyte/ gas/ electrocatalyst will be regulated, which is strongly
enforced with overpotential and charge transfer during AOR and HER. Furthermore,
constructing an electrode configuration that promotes mass transport also contributed to
electrocatalytic performance [22]. The triple phase interface of electrocatalyst-electrolyte-
gaseous analyte by tuning the surface properties can yield highly efficient electrocatalytic
performances for HER and AOR, and to drive the AOR reaction towards specific products.
1.4 Carbon incorporation
The intrinsic properties of carbon-based materials and the unique structure of
nanocarbon substrates, such as their high surface area, chemical stability, and conductivity,
make them attractive for electrocatalysts [23]. The intrinsic carbon defects including the
zigzag and armchair configurations of carbon atoms provide unique electronic structures with
delocalized electrons to promote the electrocatalytic activity. Besides, the intrinsic defects
incorporate appropriate adsorption/desorption energies for the intermediates, driving the
reaction towards selectivity. Especially, heteroatom doped carbon structures enables different
charge density on the substrates which can be tuned promptly for higher electrocatalytic
activity [23]. Since, the size or electronegativity of heteroatoms and carbon atoms is
consistently different, a modified electronic structure is manifested in the carbon layer [23].
For example, N and S doping in the carbon matrix increases active sites for intermediate
adsorption and improves the intrinsic conductivity of the carbon structures [24]. In addition,
due the difference in size and electronegativity, the carbon layer exhibits structural and
electronic defects which promotes the electrocatalytic reactions for HER and AOR,
respectively. By removing a C atom from a molecule, a vacancy/defect can be constructed,
leading not only to a loss of unity of conjugation but also to a loss of stability.
Line 1.
References:
1. Wang HF, Tang C, Li BQ, Zhang Q. A review of anion-regulated multi-anion
transition metal compounds for oxygen evolution electrocatalysis. Inorganic
Chemistry Frontiers. 2018;5(3):521-34.
2. Li BQ, Zhang SY, Tang C, Cui X, Zhang Q. Anionic regulated NiFe (oxy) sulfide
electrocatalysts for water oxidation. Small. 2017 Jul;13(25):1700610.
3. Ling T, Jaroniec M, Qiao SZ. Recent progress in engineering the atomic and
electronic structure of electrocatalysts via cation exchange reactions. Advanced
Materials. 2020 Nov;32(46):2001866.
4. Tian L, Pang X, Xu H, Liu D, Lu X, Li J, Wang J, Li Z. Cation–Anion Dual Doping
Modifying Electronic Structure of Hollow CoP Nanoboxes for Enhanced Water
Oxidation Electrocatalysis. Inorganic Chemistry. 2022 Oct 12;61(42):16944-51.
5. Peican w, and Baoguo W. Designing Self-Supported Electrocatalysts for
Electrochemical Water Splitting: Surface/ interface Engineering toward Enhanced
Electrocatalytic Performance. ACS Appl. Mater. Interfaces 2021, 13, 59593-59617.
6. Xianhong W, Yi W, Zhong-S W. Design principle of electrocatalyst for the
electrooxidation of organics, Chem 8, 2594-2629,(2022)
7. Jieqiong S, Chao Y, Shuangming C, Tulai S, Yan L, Chongzhi Z, et al. Short-Range
Ordered iridium Single Atoms Integrated into Cobalt Oxide Spinel Structure for
Highly Efficient Electrocatalytic Water Oxidation. J.Am. Chem. Soc. 2021, 143, 13,
5201-5211.
8. Wang Y, Han P, Lv X, Zhang L, Zheng G. Defect and interface Engineering for
aqueous Electrocatalytic Co2 Reduction. Joule 2018, 2, 2551-2582.
9. Zhu y, Liu X, Jin S, Chen H, Lee W, Liu M, Chen Y. Anionic Defect Engineering of
Transition Metal Oxides for Oxygen Reduction and Evolution Reaction. J. Mater.
Chem. A 2019, 7, 5875-5897.

10. Zhang H, Lv R, Defect Engineering of Two-Dimensional Materials for Efficient
Electrocatalysts. J. Materiomics 2018, 4, 95-107.
11. Li X, Wang J. One-Dimensional and Two-Dimensional Synergized Nanostructures
for High-Performing Energy Storage and Conversion. InfoMat 2020, 2, 3-32.
12. Zhang J, Li Y, Xu C, Li J, Yang L, Yin S. 2D/2D/1D Structure of a Self-Supporting
Electrocatalyst for Efficient Hydrogen Evolution. ACS Applied Energy Materials.
2022 Jan 18;5(2):1710-9.
13. Wu D, Zhang W, Cheng D. Facile synthesis of Cu/NiCu electrocatalysts integrating
alloy, core–shell, and one-dimensional structures for efficient methanol oxidation
reaction. ACS Applied Materials & Interfaces. 2017 Jun 14;9(23):19843-51.
14. Xing Z, Yang X, Asiri AM, Sun X. Three-dimensional structures of MoS2@ Ni
core/shell nanosheets array toward synergetic electrocatalytic water splitting. ACS
Applied Materials & Interfaces. 2016 Jun 15;8(23):14521-6.
15. Lee M, Ha H, Cho K H, Seo H, Park S, Lee Y H, et al. Importance of Interfacial Band
Structure between the Substrate and Mn3O4 Nanocatalysts During Electrochemical
Water Oxidation. ACS Catal. 2020, 10, 1237-1245.
16. Zhou K, Li Y. Catalyst Based on Nanocrystals with Well-defined Facets.
Angew.Chem, Int. Ed. 2012, 51, 602-613.
17. Pan J, Liu G, Lu G. Q, Cheng H.M. On the True Photo reactivity Order of{001},
{101}, and {101} Facts of Anatase TiO2 Crystals. Angew. Chem, Int. Ed. 2011, 50,
2133-2137.
18. Zhao G, Jiang Y, Dou SX, Sun W, Pan H. Interface engineering of heterostructured
electrocatalysts towards efficient alkaline hydrogen electrocatalysis. Science Bulletin.
2021 Jan 15;66(1):85-96.

19. Hu W, Shi Q, Chen Z, Yin H, Zhong H, Wang P. Co2N/Co2Mo3O8 heterostructure
as a highly active electrocatalyst for an alkaline hydrogen evolution reaction. ACS
applied materials & interfaces. 2021 Feb 8;13(7):8337-43.
20. Shi L, Yin Y, Wang S, Sun H. Rational Catalyst Design for N2 Reduction Under
Ambient Conditions: Strategy toward Enhanced Conversion Efficiency. ACS Catal.
2020, 10, 6870-6899.
21. Xiao S, Jian-H T, Bin D, Yujie S. Recent advances of Nonprecious and bifunctional
Electrocatalysts for overall Water Splitting. Sustainable Energy Fuels, 2020,4, 3211-
3228.
22. Michaela P, Jaromir H, Karel B. Electrocatalysts for the oxygen evolution reaction in
alkaline and neutral media. A comparative review. Journal of Power Sources 507
(2021) 230072.
20.[21.] Section 5. Different chemicals were displayed in this section, the AORs of all the
given chemicals are recommended to be given in this section, and theoretical potential of
each reaction should be given in these equations.
Response: We thank the reviewer for the valuable comment. As per reviewer comment, we
have added the theoretical potential of recommended anodic electrochemical reactions.
Urea oxidation
Overall reaction: CO(NH2)2 + H2O → 3H2 + N2 + CO2 Eo = 0.37 V (vs.RHE)
Anode reaction: CO(NH 2) 2 + 6OH¯ → N2 + 5H2O + CO2 + 6e¯ Eo = 0.37 V (vs.
RHE)
Methanol oxidation
Anode reaction: CH3OH + OH¯ → CO2 + 6e¯ + 5H2O Eo = 0.016 (vs.SHE)
Cathode reaction: 3/2O2 + 6e¯ + 3H2O → 6OH¯ Eo = 1.229 V (vs.SHE)

Overall reaction: CH3OH + 3/2O2 → CO2 + 2H2O Eo = 1.245 V (vs. SHE)
Hydrazine oxidation
Anode reaction: N2H4 + 4OH¯ → N2 + 4H2O + 4e¯ Eo = -0.33 V (vs.RHE)
The above-mentioned changes have been updated in the revised manuscript UOR (Page
41, Line 3), MOR ( Page 52, Line 10) and HzOR ( Page 62, Line 4).
21.[22.] Section 5.6 contained several subsections. It is confusing that why HMF, formic acid
and ethanol were classified into the group of aldehyde group?
we have revised Section 5.6 and classified based on the reductive chemicals. The important
biomass derived chemicals such as, HMF containing aldehyde and alcohol groups, furfural
with aldehyde group and glucose containing 6 carbon atoms with an aldehyde group show
prospects in AOR. All these three organic compounds with aldehyde group in their molecular
structure can be derived from the biomass and able to participate in the anodic oxidation
reactions to yield value-added products as well as reduce the potential required for the
hydrogen production in the hybrid water electrolyzer. Therefore, we have revised the titles of
the section 5.6 as given below:
5.6 Biomass-derived aldehyde assisted anodic oxidation
5.6.1 HMF Oxidation
5.6.2 Furfural Oxidation
5.6.3 Glucose Oxidation
5.7 Formic acid oxidation

The above-mentioned changes have been updated in the revised manuscript Page 64 - 83.
22.[23.] Page 57. The comparison table was dustered the oxidation species. Thus, it is
recommended to put the “oxidation species” in the first column.
we have revised the comparison table.
Comparison Table:
Tafel Current
Oxidation Potential
Electrocatalyst Electrolyte slope Density Ref.
Species (V)
(mV dec-1) (mA cm−2)
1 M KOH, 1.544
Urea P-CoNi2S4 YSSs 55 10 [80]
0.5 M urea vs. RHE
Ni/NiO-N-C- 1 M KOH, 0.6

Urea - 182
500 0.33 M urea vs. SCE [81]
U-NiMn-LDH/ 0.5 M KOH, 1.351

Urea 38.9 20 [84]
CFC 0.5 M urea vs. RHE
Ni-NiO/Gr - 0.5 M KOH, 0.5

Urea 35.9 38.24 [109]
450⁰C 0.5 M urea vs. SCE
1 M KOH, 0.41
Urea NiCo LDH 45 10 [120]
0.33 M Urea vs. Hg/HgO
Mo-
1 M KOH, 1.29
Urea NiCoP@NiCoP/ _ 100 [83]
0.5 M urea vs. RHE
NiXCoYH2PO2
1 M KOH, 1.36
Urea NiF3/Ni2P@CC 33 10 [86]
0.33 M Urea vs. RHE
1 M KOH, 1.43
Urea β- Ni(OH)2 125 0.5 [81]
0.33 M Urea vs. RHE
1 M KOH, 1.31
Urea NiCo-BDC 58.15 10 [121]
0.33 M Urea vs. RHE
NiFe-MIL-53- 1 M KOH, 1.398 V

Urea 14 50 [122]
NH2 0.33 M Urea. vs. RHE
1 M KOH, 1.39 V vs.

Urea NiS nanotube 23.62 100 [123]
0.33 M Urea RHE
1 M KOH, 1.3 V vs.

Urea NiS2/MoO2 37.4 10 [124]
0.33 M urea RHE
1 M KOH, 0.33 0.6 V vs.

Urea Ni(OH)2 36 142 [125]
M Urea Ag/AgCl
F-doped 2D 1 M KOH, 1.16 V vs.

Urea 29.367 10 [12]
Ni(OH)2 NSs 0.33 M Urea RHE
1 M KOH, 1.39 V vs.

Urea Fe2GeO4 79 10 [85]
0.33 M urea RHE
1 M KOH, 1.42 V vs.

Urea Co2GeO4 76 10 [85]
0.33 M urea RHE
1 M
0.7 V vs.
Urea NiCo LDH-1 KOH, ).33 M 45 116 [133]
Hg/HgO
Urea
1 MM KOH, 1 0.28 V vs.

Ethanol Co-Bi@rGO - 10.25 [90]
M Ethanol SCE
1 M KOH 0.1 0.5 V vs. 9365.9 mA mg-

Ethanol Pd7Ag3 Ns/C - [91]
1
M Ethanol Hg/HgO pd
1 M KOH, 1 M 0.5 V vs.

Ethanol PdZn/NC@ ZnO - [13]
Ethanol Ag/AgCl 20
L12Pd3Sn 1 M KOH, 1 1.25 V vs.

Ethanol - 6.22 A mgpd-1 [126]
nanorod M Ethanol RHE
0.5 M H2SO4, 1 1.25 V vs.

Ethanol PtSn/SnOx/CNT - 10 [127]
M Ethanol RHE
Ethanol GC/ 1 M NaOH, 1 0.7 V vs. - 1172 A g-1Pd [128]

Co3(Co(CN)6)2/
M Ethanol. Hg/HgO
Pd
[UO2 (3-OMe-t- 0.5 M H2SO4, 1.06 V vs.

Ethanol - 32.93 [129]
salcn) H2O] PtSn 1 M ethanol RHE
1 M KOH, -0.5
Ethanol Ts-Pd/C - 3.22 [130]
1 M ethanol vs. SCE
1 M KOH, 1.53
Methanol NiO/NF 135 100 [97]
1 M MeOH vs. RHE
1 M KOH, 0.30
Methanol ZCZMMO/GCE - 414 mA mg−1 [98]
1 M MeOH vs. Ag/AgCl
1 M KOH, 0.6
Methanol Cu (OH)2/CuO - 53 [99]
0.5 M MeOH vs. Hg/HgO
NiNH2BDCMO 1 M NaOH 0.69

Methanol 60.8 267.7 [100]
F/5 wt %rGO 0.3 M MeOH vs. Hg/HgO
Pd@Rh0.07 Pd 1 M KOH, 0.695

Methanol 53 200 A g-1 [101]
NDs 0.5 M MeOH vs. RHE
Nitric oxide 0.5 M H2SO4, 1.07

P-CC 52 10 [15]
(NO) NO gas flow vs. RHE
1 M KOH, 1.6
Nitrogen ZnFe0.4CO1.6O4 - 10 [102]
N2 gas flow vs. RHE
0.1 M Na2SO4, 2.2

Nitrogen Ru/TiO2 - 4.5 [103]
N2 gas flow vs RHE
1 M KOH, 22 mV
Hydrazine CoxP@CO3O4 - 10 [104]
0.3M hydrazine vs. RHE
Ni3N-Co3N 1 M KOH, -88 mV

Hydrazine 35.1 10 [131]
PNSs/NF 0.2 M N2H4 vs. RHE
1 M KOH, 0.25
Hydrazine Ni@NiP3.0/C - 2675.1 A gNi-1 [132]
1 M hydrazine vs. RHE
23.[24.] Conclusion should be rewritten. The first paragraph was full of mistakes. Value-
added products formation was not found in the manuscript. Perspectives should be given
in the conclusion to guide the readers working in the field.
The hybrid water electrolysis integrated with anode oxidation reaction (AOR) is a
promising technique to replace the sluggish oxygen evolution reaction (OER). In this review,
the most significant advantages of the recent developments of electrocatalytic hydrogen
production technology through the hybrid water electrolysis method is discussed. The hybrid
water electrolysis method achieves a very small overpotential and higher exchange current
densities. Compared to OER, alternative oxidation reactions with lower thermodynamic
concern can not only reduce the amount of energy needed to produce H 2 and eliminate
potential safety issues resulting from gas crossovers and membrane degradation, but also
benefit the economy and the environment tremendously. Agricultural waste, industrial
wastewater, plant/animal residues, and daily sewage are examples of biomass feedstocks and
industrial pollutants with abundant reserves that can be used as anodic substance. By
converting trash into nontoxic compounds or converting them into value-added products, the
HWE system can achieve a benign cycle from trash to treasure while generating green H 2.
The review summarizes the recent development of the electrocatalyst activities composed
of noble metal, non-noble metal, and carbon-based materials and the investigation of various
probable anodic reactions and the corresponding activity in the different electrolytes. The
non-noble metal-based electrocatalyst, due to its abundance, low cost, excellent activity, and
good stability, are expected to be the potential candidate for hybrid water electrolysis. Next,
the electrooxidation of various chemical species assisted eco-friendly hydrogen production

are briefly discussed. The energy saving, value-added and cost-effective anodic oxidation
reaction in hybrid water electrolysis for production of high purity hydrogen are discussed.
The electrocatalyst can suffer from poisoning issues for desorption and adsorption of the
organic compounds to produce hydrogen and valuable products. Substituting sluggish OER
by employing various organic product oxidation reactions has also been extended to other
electrocatalytic areas such as nitrogen reduction (NRR), CO2 reduction reaction (CO2RR),
and oxygen reduction reaction (ORR). The following critical aspects provide important
research perspectives on the hybrid water electrolysis technique.
1. In order to achieve a low cost, efficient hydrogen production systems, replacing the
conventional water electrolysis method with hybrid water electrolysis using anodic
oxidation reactions (AOR) are highly anticipated. OER is replaced by the anodic
oxidation of diverse organic products over carefully engineered electrocatalysts as
anodes. This review on hybrid water electrolysis is expected to provide strategies for
improved anode oxidation as an excellent alternative technology for traditional water
splitting and achieve further potential applications.
2. The crucial part is to identify the ideal anode material related to the structure and the
electrocatalytic activity. Attention should be given to the material design involving
structures, composites, defect engineering, and the surface modification of the
interlayers that have great potential to behave as highly active anodes.
3. The earth-abundant transition metals are receiving more attention as electrodes in
anodic oxidation (AOR). The recent developments in operating techniques have been
applied to inspect the evolution of electrocatalyst intermediates in real time during the
anodic oxidation process because of inevitable reconstruction of electrocatalysts
during anodic oxidation.

4. According to most reports, electrocatalysts for above anodic reactions are normally
active for OER, which results in low selectivity and small electrochemical window for
hybrid water electrolysis systems. Hence, understanding the difference between AOR
and OER is crucial for controlling and manipulating the selectivity of the desired
products.
5. To maximize the electrocatalytic performance of the anode material, it is necessary to
optimize the electrocatalytic condition during the oxidation process. The electrolyte
concentration and analyte concentration, pH, the presence or absence of metallic
cations, and temperature influence the anode oxidation of the chemical species. The
alkaline medium with abundant OH¯ ions and the other radical species makes the
electrocatalyst more active towards AOR. Therefore, electrocatalytic anodic reactions
can be optimized by varying the mentioned parameters in the electrochemical system.
6. It remains a challenge to the general scientific understanding of the oxidation of
chemical species and organic pollutants into value-added products. There is no
standard way to measure electrocatalyst performance in AOR and the prominent
reaction pathways. For example, adsorption and/or desorption ability of the functional
groups (-OH, -NH2, -CO, -CHO, etc.), and free energy of primary intermediate over
electrocatalyst surface. Thereby, utilizing theoretical modelling and simulation of the
electrocatalyst surface can provide appropriate formation energies of the
intermediates and a suggested reaction pathway. Therefore, the reaction mechanism
for the organic product oxidation by AOR needs to be further evaluated using
experimental and theoretical studies.
7. Modern advanced ex situ and in situ techniques such as XRD, X-ray absorption
spectroscopy, XPS, Raman spectroscopy, liquid and gas chromatography are in great
demand to investigate the composition, and structure changes of electrocatalysts

during the electrochemical reaction and quantitatively determine the products at both
anode and cathode.
we have revised the manuscript.
[25.] Page 59, line 49-59; Page 60, line 9-15. These two parts were still the statement of
present research and can not be considered as the “additional research focus”.
we revised the manuscript with few aspects that can be considered as the major research
focus of hybrid water electrolysis in future. The critical aspects that need to be focused more
on future for the further development of hybrid water electrolysis are given below.
1. In order to achieve a low cost, efficient hydrogen production systems, replacing the
conventional water electrolysis method with hybrid water electrolysis using anodic
oxidation reactions (AOR) are highly anticipated. OER is replaced by the anodic
oxidation of diverse organic products over carefully engineered electrocatalysts as
anodes. This review on hybrid water electrolysis is expected to provide strategies for
improved anode oxidation as an excellent alternative technology for traditional water
splitting and achieve further potential applications.
2. The crucial part is to identify the ideal anode material related to the structure and the
electrocatalytic activity. Attention should be given to the material design involving
structures, composites, defect engineering, and the surface modification of the
interlayers that have great potential to behave as highly active anodes.

3. The earth-abundant transition metals are receiving more attention as electrodes in
anodic oxidation (AOR). The recent developments in operating techniques have been
applied to inspect the evolution of electrocatalyst intermediates in real time during the
anodic oxidation process because of inevitable reconstruction of electrocatalysts
during anodic oxidation.
4. According to most reports, electrocatalysts for above anodic reactions are normally
active for OER, which results in low selectivity and small electrochemical window for
hybrid water electrolysis systems. Hence, understanding the difference between AOR
and OER is crucial for controlling and manipulating the selectivity of the desired
products.
optimize the electrocatalytic condition during the oxidation process. The electrolyte
concentration and analyte concentration, pH, the presence or absence of metallic
cations, and temperature influence the anode oxidation of the chemical species. The
alkaline medium with abundant OH¯ ions and the other radical species makes the
electrocatalyst more active towards AOR. Therefore, electrocatalytic anodic reactions
can be optimized by varying the mentioned parameters in the electrochemical system.
6. It remains a challenge to the general scientific understanding of the oxidation of
chemical species and organic pollutants into value-added products. There is no
standard way to measure electrocatalyst performance in AOR and the prominent
reaction pathways. For example, adsorption and/or desorption ability of the functional
groups (-OH, -NH2, -CO, -CHO, etc.), and free energy of primary intermediate over
electrocatalyst surface. Thereby, utilizing theoretical modelling and simulation of the
electrocatalyst surface can provide appropriate formation energies of the
intermediates and a suggested reaction pathway. Therefore, the reaction mechanism

for the organic product oxidation by AOR needs to be further evaluated using
experimental and theoretical studies.
demand to investigate the composition, and structure changes of electrocatalysts
during the electrochemical reaction and quantitatively determine the products at both
anode and cathode.
24.[26.] Page 60, line 2-3. “However,” should be deleted.
corrected the revised manuscript. To maximize the performance of the anodic electrocatalyst,
it is necessary to optimize the electrocatalytic condition during the oxidation process. The
electrolyte concentration and analyte concentration, pH, the presence or absence of metallic
cations, and temperature influences the anodic oxidation of the chemical species.
20.
25.[27.] Page 60, line 19-20. What are the “value added products” refer to?
Response: We thank the reviewer for the valuable comment. In hybrid water electrolysis
technology, HER is manifested at the cathode assisted by the counter oxidative reactions at
the anode. By the reduced theoretical potential for AOR at anode, a higher H 2 production can
be elucidated at the cathode at a comparatively lower cell potential than with OER. Besides,
value-added products can be produced at the anode by introducing suitable chemical species
into the anode chamber. The value-added products are generally chemicals with high
monetary value than the unoxidized chemical species [1, 2]. For example, nitric acid is the
value-added product with high monetary value produced from the anodic oxidation of
abundant N2 [1]. Besides, specific value-added products can be produced by an appropriate
choice of oxidative species. For example, furfural, HMFCA, and furoic acid can be
specifically produced by anodic oxidation of HMF depending on the number of electron
transfer steps. Similarly, nitric acid and formic acid are the oxidative reaction products of N 2
and glycerol, respectively. The application of value-added products produced from hybrid
water electrolysis technology include nitrate which is used to produce fertilizers, gunpowder,
and explosives, HMFCA which is used as furanic polyester interleukin inhibitor and furoic
acid used in organic synthesis of medicines, perfumes, and furoate esters.
20.
References
[1] Kuang M, Wang Y, Fang W, Tan H, Chen M, Yao J, Liu C, Xu J, Zhou K, Yan Q.
Efficient Nitrate Synthesis via Ambient Nitrogen Oxidation with Ru-Doped TiO2/RuO2
Electrocatalysts. Advanced Materials 2020;32(26):2002189.
[2] Chadderdon XH, Chadderdon DJ, Pfennig T, Shanks BH, Li W. Paired electrocatalytic
hydrogenation and oxidation of 5-(hydroxymethyl)furfural for efficient production of
biomass-derived monomers. Green Chemistry 2019;21(22):6210-9.
26.[28.] Page 60, line 29-30. What kind of efforts should be made? The “efforts” should be
elaborated more specifically.
we have mentioned further efforts to develop a more efficient and low-cost hybrid water
electrolysis method. Novel electrocatalyst design and efficient synthesis approach, choice of
electrolyte, advanced theoretical studies, and ex-situ/in-situ operations are some of the
important strategies to increase viability for hybrid water electrolysis technology.
1. The earth-abundant transition metals are receiving more attention as electrodes in anodic
oxidation (AOR). The recent developments in operating techniques have been applied to
inspect the evolution of electrocatalyst intermediates in real time during the anodic
oxidation process because of inevitable reconstruction of electrocatalysts during anodic
oxidation.
optimize the electrocatalytic condition during the oxidation process. However, the
electrolyte concentration and analyte concentration, pH, the presence or absence of
metallic cations, and temperature influence the anode oxidation of the chemical species.
3. It remains a challenge to the general scientific understanding of the oxidation of chemical
species and organic pollutants into value-added products. The alkaline medium with
abundant OH¯ ions and the other radical species makes the electrocatalyst more active in
the anode oxidation. And therefore, the AOR process discussion needs to be further
evaluated using experimental and theoretical studies.
demand to investigate the composition, and structure changes of electrocatalysts during
the electrochemical reaction and quantitatively determine the products at both anode and
cathode.
Line 9.
27.[29.] Page 29, line 9-10. “Following” should be deleted.
we have revised the manuscript as “Wang et al. [1] synthesized Ni-based W doped
homogeneous electrocatalyst for urea oxidation as shown in the Fig. 8(a).”
Line 10.

Response To Reviewer Comments

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Response To Reviewer Comments

Uploaded by

Copyright:

Available Formats

Response to Reviewer Comments: (Manuscript Number: RSER-D-22-04203)

Renewable and Sustainable Energy Reviews

comments/suggestions to improve the quality of our recent submission

for the consideration of publication by Renewable and Sustainable Energy

track changes for all responses to the reviewer’s comments.

2. Submit the clean revised version of the manuscript.

the manuscript with appropriate response to the reviewer’s comments.

(e.g. line number X to Y on page X in the marked-up manuscript) in this response.

4. Read the 'Guide for Authors' at https://www.elsevier.com/journals/renewable-and-

sustainable-energy-reviews/1364-0321/guide-for-authors very carefully. It is the sole

addresses, article structure, keywords, abbreviations, nomenclature, captions on figures

and layout format as mentioned in the Guide for Authors.

mentioned figures, graphics, and images in the manuscript.

see http://webshop.elsevier.com/languageediting However, using an English language

service (including Elsevier's) is NOT a guarantee that an article will be subsequently

accepted for publication.

Authors' and 'Publishing Ethics' at

https://www.elsevier.com/about/our-business/policies/publishing-ethics and 'Ethical

guidelines for journal publication' at

CrossRef visit their website at http://www.crossref.org/crosscheck.html

production to be include in this section.

power generation [2]. Currently, 75 Mt of pure H 2 and 45 Mt of mixed gases with H 2 is

of chemical elements for renewable energy. RSC Advances 2012;2(21):7933-47.

MZ, Eikerling M, Staffell I, Balcombe P, Shao-Horn Y, Schäfer H. Water electrolysis: from

Society Reviews 2022;51(11):4583-762.

[5] Yan Y, Xia BY, Zhao B, Wang X. A review on noble-metal-free bifunctional

heterogeneous catalysts for overall electrochemical water splitting. Journal of Materials

2. Figure 2 should be further elaborated in text.

a high theoretical potential of 1.23 V [3].

M-OH + OH¯ → M-O + H2O (1)

2M-O → 2M + O2(g) (2)

oxygen species adsorption on catalyst surfaces or electrochemical reactions. The formed

In this system, biomass-derived aldehyde oxidation platform chemicals such as 5-

OER shown in Fig. 2R1.

P, Li W, Wang Y, Chen R, Zou Y, Fu X-Z, Li Y, Duan X, Wang S. Combined anodic and

Nature Catalysis 2022;5(1):66-73.

Oxidation Reactions in Alkaline Media. Advanced Functional Materials

Oxidation: From Electrolysis via Homogeneous to Biological Catalysis. ChemCatChem

with (photo)electrochemical fuel production reactions. Nature Communications

[6] Yan Y, Xia BY, Zhao B, Wang X. A review on noble-metal-free bifunctional

heterogeneous catalysts for overall electrochemical water splitting. Journal of Materials

[7] Artero V, Chavarot-Kerlidou M, Fontecave M. Splitting Water with Cobalt. Angewandte

Chemie International Edition 2011;50(32):7238-66.

we have corrected the typo mistakes in the revised manuscript.

infrastructure sustainability by converting them into commercially relevant compounds.

reference in the revised manuscript. Conversion of renewable biomass derivatives to

applications, furfural is a promising biomass-derived synthetic platform species to produce

with increasing molar ratio of oxygen to carbon [2, 31, 2].

1. Li G, Naveen A, Alex R, Adam H, Michael J, Density functional theory study of furfural

electrochemical oxidation on the Pt (111) surface. Journal of Catalysts,2019.373: p.322-

Rare Metals, 2022. 41(3): p. 836-843.

we have corrected the graphical abstract in the revised manuscript.

manuscript very carefully to avoid similar errors.

suggestion, we carefully revised the manuscript to avoid the above-mentioned errors.

systems as listed below.

1. Electrochemical water splitting for highly efficient hydrogen (H 2) production can be

of energy consumption [1].

return of energy investment [2].

OER with thermodynamically more favorable AOR [2].

[1] Li Y, Wei X, Han S, Chen L, Shi J. MnO2 Electrocatalysts Coordinating Alcohol

Oxidation for Ultra-Durable Hydrogen and Chemical Productions in Acidic Solutions.

Angewandte Chemie International Edition 2021;60(39):21464-72.