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CO2 Hydrogenation Catalysis
CO2 Hydrogenation Catalysis
Edited by
Yuichiro Himeda
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10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xi
1 Introduction 1
Yuichiro Himeda and Matthias Beller
1.1 Direct Use of CO2 1
1.2 Chemicals from CO2 as a Feedstock 2
1.3 Application and Market Studies of CO2 Hydrogenation Products 4
1.3.1 Formic Acid/Formate 4
1.3.2 Methanol 4
1.3.3 Methanation 5
1.3.4 Energy Storage 6
1.4 Supply of Materials 6
1.4.1 CO2 Supply 6
1.4.2 Energy and H2 Supply 8
1.5 Political Aspect: Tax 9
1.6 Conclusion and Perspectives 9
References 10
2 Homogeneously Catalyzed CO2 Hydrogenation to Formic Acid/Formate

by Using Precious Metal Catalysts 13
Wan-Hui Wang, Xiujuan Feng and Ming Bao
2.1 Introduction 13
2.2 Ir Complexes 14
2.2.1 Ir Complexes with N,N-ligands 14
2.2.1.1 Tautomerizable N,N-ligands with OH Groups 14
2.2.1.2 N,N-ligands with NH Group 30
2.2.1.3 Tautomerizable N,N-ligands with OH and NH Groups 32
2.2.1.4 Tautomerizable N,N-ligands with Amide Group 33
2.2.2 Ir Complexes with C,N- and C,C-ligands 34
2.2.3 Ir Complexes with Pincer Ligands 35
2.3 Ru Complexes 37
2.3.1 Ru Complexes with Phosphorous Ligands 38
vi Contents
2.3.2 Ru Complexes with N,N- and N,O-ligands 40

2.3.3 Ru Complexes with Pincer Ligands 41
2.4 Rh Complexes 46
2.5 Summary and Conclusions 49
References 49
3 Homogeneously Catalyzed CO2 Hydrogenation to Formic Acid/Formate with

Non-precious Metal Catalysts 53
Luca Gonsalvi, Antonella Guerriero and Sylwia Kostera
3.1 Introduction 53
3.2 Iron-Catalyzed CO2 Hydrogenation 55
3.2.1 Non-pincer-Type Iron Complexes 56
3.2.2 Pincer-Type Iron Complexes 63
3.3 Cobalt-Catalyzed CO2 Hydrogenation 69
3.4 Nickel-Catalyzed CO2 Hydrogenation 73
3.5 Copper-Catalyzed CO2 Hydrogenation 77
3.6 Manganese-Catalyzed CO2 Hydrogenation 78
3.7 Other Non-precious Metals for CO2 Functionalization 81
3.8 Conclusions and Perspectives 85
References 86
4 Catalytic Homogeneous Hydrogenation of CO2 to Methanol 89

Sayan Kar, Alain Goeppert and G. K. Surya Prakash
4.1 Carbon Recycling and Methanol in the Early Twenty-First Century 89
4.2 Heterogeneous Catalysis for CO2 to Methanol 91
4.3 Homogeneous Catalysis – An Alternative for CO2 to Methanol 92
4.3.1 Benefits of Homogeneous Catalysis 92
4.3.2 CO2 Hydrogenation to Methanol Through Different Routes 92
4.3.3 The First Homogeneous System for CO2 Reduction to Methanol 93
4.3.4 Indirect CO2 Hydrogenation 94
4.3.5 Direct CO2 Hydrogenation 97
4.3.5.1 Through Formate Esters 97
4.3.5.2 Through Oxazolidinone or Formamides 100
4.3.6 CO2 to Methanol via Formic Acid Disproportionation 108
4.4 Conclusion 109
References 110
5 Theoretical Studies of Homogeneously Catalytic Hydrogenation of Carbon

Dioxide and Bioinspired Computational Design of Base-Metal Catalysts 113
Xiuli Yan and Xinzheng Yang
5.1 Introduction 113
5.2 H2 Activation and CO2 Insertion Mechanisms 114
5.2.1 Hydrogen Activation 114
5.2.2 Insertion of CO2 115
Contents vii
5.3 ydrogenation of CO2 to Formic Acid/Formate

H 118
5.3.1 Catalysts with Precious Metals 118
5.3.2 Catalysts with Non-noble Metals 128
5.4 Hydrogenation of CO2 to Methanol 133
References 145
6 Heterogenized Catalyst for the Hydrogenation of

CO2 to Formic Acid or Its Derivatives 149
Kwangho Park, Gunniya Hariyanandam Gunasekar and Sungho Yoon
6.2 Molecular Catalysts Heterogenized on the Surface of Grafted Supports 150
6.3 Molecular Catalysts Heterogenized on Coordination Polymers 157
6.4 Molecular Catalysts Heterogenized on Porous Organic Polymers 161
6.5 Concluding Remarks and Future Directions 172
References 173
7 Design and Architecture of Nanostructured Heterogeneous Catalysts

for CO2 Hydrogenation to Formic Acid/Formate 179
Kohsuke Mori and Hiromi Yamashita
7.2 Unsupported Bulk Metal Catalysts 180
7.3 Unsupported Metal Nanoparticle Catalysts 181
7.3.1 Metal Nanoparticles Without Stabilizers 181
7.3.2 Metal Nanoparticles Stabilized by Ionic Liquids 182
7.3.3 Metal Nanoparticles Stabilized by Reverse Micelles 183
7.4 Supported Metal Nanoparticle Catalysts 184
7.4.1 Metal Nanoparticles Supported on Carbon-Based Materials 184
7.4.2 Metal Nanoparticles Supported on Nitrogen-Doped Carbon 185
7.4.3 Metal Nanoparticles Supported on Al2O3 189
7.4.4 Metal Nanoparticles Supported on TiO2 191
7.4.5 Metal Nanoparticles Supported on Surface-Functionalized Materials 194
7.5 Embedded Single-Atom Catalysts 198
References 203
8 Heterogeneously Catalyzed CO2 Hydrogenation to Alcohols 207

Nat Phongprueksathat and Atsushi Urakawa
8.2 CO2 Hydrogenation to Methanol – Past to Present 207
8.2.1 Syngas to Methanol 207
8.2.2 CO2 to Methanol 208
8.2.3 Thermodynamic Consideration – Chemical and Phase Equilibria 212
8.2.4 Catalyst Developments 215
8.2.5 Active Sites and Reaction Mechanisms: The Case of Cu/ZnO Catalysts 217
viii Contents
8.2.6 Beyond Industrial Cu/ZnO/Al2O3 Catalysts 223

8.3 O2 Hydrogenation to Ethanol and Higher Alcohols – Past to Present 226
C
8.3.1 Background 226
8.3.2 Catalysts, Active Sites, and Reaction Mechanisms 227
8.3.2.1 Modified-Methanol Synthesis Catalyst 227
8.3.2.2 Modified Fischer–Tropsch Catalysts 230
8.3.2.3 Rhodium-Based Catalysts 231
8.3.2.4 Modified Molybdenum-Based Catalysts 232
8.4 Summary 232
References 233
9 Homogeneous Electrocatalytic CO2 Hydrogenation 237

Cody R. Carr and Louise A. Berben
9.1 CO2 Reduction to C─H Bond-Containing Compounds: Formate or Formic
Acid 237
9.1.1 Survey of Catalysts 238
9.1.1.1 Group 9 Metal Complexes 238
9.1.1.2 Group 8 Metal Complexes 241
9.1.1.3 Nickel Complexes 244
9.1.1.4 Iron and Iron/Molybdenum Clusters 246
9.1.2 Hydride Transfer Mechanisms in CO2 Reduction to Formate 247
9.1.2.1 Terminal Hydrides 247
9.1.2.2 Bridging Hydrides 248
9.1.3 Kinetic Factors in Catalyst Design 249
9.1.3.1 Roles of Metal–Ligand Cooperation 249
9.1.3.2 Roles of Multiple Metal–Metal Bonds 250
9.1.4 Thermochemical Considerations in Catalyst Design 253
9.1.4.1 Selectivity for Formate over H2 as a Function of Hydricity 254
9.1.4.2 Solvent Dependence of Hydricity 255
9.2 Prospects in Electrocatalysis: CO2 Reduction Beyond Formation of One C─H
Bond 255
References 257
10 Recent Advances in Homogeneous Catalysts for Hydrogen Production

from Formic Acid and Methanol 259
Naoya Onishi and Yuichiro Himeda
10.2 Formic Acid Dehydrogenation 260
10.2.1 Organic Solvent Systems 260
10.2.1.1 Ru 260
10.2.1.2 Ir 266
10.2.1.3 Fe 268
Contents ix
10.2.2 Aqueous Solution Systems 270

10.2.2.1 Ru 270
10.2.2.2 Ir 272
10.3 Aqueous-phase Methanol Dehydrogenation 275
10.3.1.1 Ir 279
10.3.1.2 Non-precious Metals 279
10.4 Conclusion 281
References 282
Index 285
xi
Preface
Carbon dioxide is widely considered to be primarily responsible for global climatic changes.
Presently, scientists are facing enormous challenges in mitigating the global CO2 emis-
sions. Significant progress has recently been achieved in the research topic of the catalysis
of CO2 hydrogenation, as one of the most important subjects in chemistry. In addition, the
paradigm shift from fossil fuels to low‐carbon renewable energy (solar photovoltaics and
wind) in recent years will allow for the competition between the CO2 emission by energy
consumption and its fixation by CO2 conversion. In future, advancement in the fields of
carbon capture and utilization is expected.
I would like to thank all the authors, who are all acknowledged as world expert in their
area of CO2 hydrogenation, for their enthusiastic efforts to present recent advances in CO2
hydrogenation. Their state‐of‐the‐art research gives exceptionally beneficial information to
the researchers, teachers, and students who are interested in the research field of CO2
hydrogenation. I anticipate that their contributions will stimulate further study in CO2
utilization as well as CO2 hydrogenation. I would also like to thank the Wiley‐VCH team for
their continuous support. Finally, I deeply appreciate the members of my research group
for their valuable assistance, especially Dr. Ryoichi Kanega for the cover design, and Dr.
Hide Kambayashi for data survey.
In the spring and summer of 2020, the world has been hit by the COVID‐19 pandemic.
Despite these difficult times, I am delighted that this book could be completed.
July 2020 Yuichiro Himeda

National Institute of Advanced
Industrial Science and Technology,
Global Zero Emission Research Center,
Tsukuba, Japan
1
Introduction
Yuichiro Himeda1 and Matthias Beller2
1
National Institute of Advanced Industrial Science and Technology, Global Zero Emission Research Center, AIST Tsukuba
West, 16-1 Onogawa, Tsukuba, Ibaraki, 305-8569, Japan
2
Leibniz-Institut für Katalyse, Applied Homogeneous Catalysis, Albert-Einstein Straße 29a, 18059, Rostock, Germany
Of the final products of the combustion of carbon-based fossil fuels, carbon dioxide (CO2)
has the highest oxidation state and is known as the major cause of global warming. Annual
CO2 emissions from anthropogenic activity in 2018 were approximately 33.1 Gton, an
increase of 1.7% compared with 2017 [1]. Since the Industrial Revolution, two trillion tons
of CO2 have accumulated in the atmosphere, and the current atmospheric concentration of
CO2 has reached an unprecedented level of over 400 ppm (Figure 1.1) [2]. The anthropo-
genic emission of CO2 is associated with energy consumption, i.e. the combustion of car-
bon-based fossil fuels, which currently account for around 85% of the world’s energy.
According to the Paris Agreement of the United Nations, an overall limit on total cumu-
lative CO2 emissions is crucial for our future development [3, 4]. According to the 2 °C
scenario, further cumulative emissions should be limited to below one trillion ton of CO2.
The spread of renewable energy (35%), advances in energy conservation (40%), and carbon
capture and sequestration (CCS) technologies (14%) are sure to contribute to addressing
the problem (Figure 1.2) [3]. However, it is clear that these methods will not completely
solve the issues arising from the vast quantities of emitted CO2. In 2017, the International
Energy Agency (IEA) presented the Energy Technology Perspectives (Beyond 2 °C Scenario:
B2DS), which placed a much greater emphasis on the role of CO2 utilization for reducing
emissions [3]. Indeed, in the next decade, we will still rely on carbon-based products for
fuels, polymers, commodity chemicals, cosmetics, detergents, and fabrics in modern life. If
these chemicals were to be derived from CO2 instead of fossil oils, a sustainable carbon
cycle will be possible.
1.1 Direct Use of CO2
Apart from chemical applications, already today, CO2 is used directly in enhanced oil
recovery (EOR), beverage carbonation, food processing (e.g. coffee decaffeination and
CO2 Hydrogenation Catalysis, First Edition. Edited by Yuichiro Himeda.

© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
2 1 Introduction
420
CO2 Concentration/ppm
400
380
360
340
320
300
1960 1980 2000 2020
Year
Figure 1.1 Atmospheric CO2 concentration at Mauna Loa Observatory. Source: Data from National
Oceanic and Atmospheric Administration, Global Monitoring Laboratory [2].
50
Reference Technology Scenario

40
Renewables
Gton of CO2
30
Efficiency
2 °C Scenario
20
Fuel switching CCS
10
Nuclear
0
2014 2020 2030 2040 2050 2060
Year
Figure 1.2 IEA 2 °C Scenario (2DS) in Energy Technology Perspectives 2017. Source: Data from
Market-driven future potential of Bio-CC(U)S [3].
drinking water abstraction), welding, as a cleaning agent for textiles, and as a solvent in the
electronics industry [5]. These approaches are commercially viable. In particular,
70–80 Mton of CO2 is consumed for EOR in the oil sector. Although such direct utilization
of CO2 addresses a significant amount of CO2 emissions, these topics are beyond the scope
of this book.
1.2 Chemicals from CO2 as a Feedstock

CO2 has been recognized as an inexpensive and abundant industrial C1 carbon source. The
various chemicals that can be produced by CO2 conversion are shown in Table 1.1 [6]. The
largest chemical use of CO2 is in the production of urea from ammonia. However, since a
1.2 Chemicals from CO2 as a Feedstock 3
Table 1.1 Chemicals produced commercially from CO2 .
Chemical Scale of production/ton
Anthropogenic CO2 emissions (2018) 33 100 000 000

Urea [7] 181 000 000
Diphenyl carbonate (Asahi Kasei Process) [8] 1 070 000
Salicylic acid 90 000
Cyclic carbonate 80 000
Polypropylene carbonate 76 000
Acetylsalicylic acid 16 000
Methanol (CRI process) [9] 4000
Source: From Omae [6]. © 2012 Elsevier.
huge amount of CO2 is emitted during methane steam reforming to supply H2, urea pro-
duction does not contribute to carbon sequestration at present.
The catalytic copolymerization of CO2 with epoxides, which provides a thermodynamic
driving force due to the strained three-membered ring, is the most prominent example of
the synthesis of CO2-based polymers without formal reduction of the carbon oxidation
state. Another example, the manufacture of diphenyl carbonate from ethylene oxide, bis-
phenol A, and CO2 instead of phosgene was developed beginning in 1977 by Asahi Kasei
Chemical Corporation to address environmental and safety issues. The first commercial
facility started operation in 2002 [8]. This process produces high-quality polycarbonate and
high-purity monoethylene glycol in high yields without waste or wastewater. In addition,
the phosgene-free process emits approximately 2.32 ton/tonPC less CO2 than the phosgene
process according to life-cycle assessment (LCA). Diphenyl carbonate has a large market
(3.6 Mton in 2016) for use in automotive parts and accessories, glazing, and medical devices.
The phosgene-free technology has already been licensed to Taiwan, South Korea, Saudi
Arabia, China, and Russia.
Since 2011, in Iceland, carbon recycling international (CRI) operated the first commer-
cial plant for methanol production from CO2 via syngas by the reverse water-gas shift
(rWGS) reaction (George Olah Renewable Methanol Plant) [9]. At present, more than five
million liters of methanol per year is produced using low-cost electricity and high-concen-
tration CO2 in the flue gas from an adjacent geothermal power plant. It should be noted
that this technology is at present only viable in Iceland; however, if there is a surplus of
green electricity in the future from an excess of renewable energy, then this process will be
attractive at other places, too.
Notably, the amount of CO2 utilized by all these approaches, including urea and carbon-
ate production, is very small compared with the magnitude of anthropogenic emissions.
Therefore, CO2 conversion into chemicals is unlikely to significantly reduce emissions.
Comparatively, it should be noted that fuels are produced and consumed on a much larger
scale than these chemicals.
4 1 Introduction
1.3 Application and Market Studies of CO2

Hydrogenation Products
Hydrogenation of CO2 could be an efficient option for developing more environment-

friendly products as alternatives to fossil-based ones. In terms of practicality, the distribu-
tion infrastructure of carbon-based chemicals is well established. However, their
manufacturing is currently several times more expensive than their conventionally pro-
duced counterparts, mainly due to the costs associated with H2 production. Some of the key
features of CO2 hydrogenation products and conventional fuels are given in Table 1.2.
1.3.1 Formic Acid/Formate

Formic acid is the first carboxylic acid and is naturally occurring produced by ants, bees,
and some plants. In 2016, the global production of formic acid was 1.02 Mton [10]. The
general production process of formic acid involves the formal carbonylation of water in a
two-step synthesis via methyl formate. Formic acid and its salts (formate) are valuable
chemical products used for silage and animal feed (27%), leather and tanning (22%), phar-
maceuticals and food chemicals (14%), textile (9%), natural rubber (7%), and drilling fluids
(4%) [11]. Recently, formic acid has been recognized as a promising liquid organic H2 car-
rier (LOHC) because of its low toxicity, low combustibility, stability, environmental friend-
liness, and 4.4 wt% (53 g l−1) H2 content [12–14]. In addition, compressed hydrogen gas can
be supplied only by heating of formic acid using catalysts as a chemical compressor [15].
Therefore, advances in the efficient production of formic acid/formates may eventually
lead to their large-scale use as LOHCs (see Chapter 10).
1.3.2 Methanol
Methanol, the industrial production of which is mainly from syngas, is in high global
demand as a fuel and bulk chemical (Figure 1.3) [17]. One ton of methanol produced by the
Table 1.2 Characteristics of various energy vectors.
Energy Approx. price

density per energy Boiling point/ Ignition point/ Vapor pressure
Compound (GJ m−3) (US$/GJ) melting point (°C) flash point (°C) at 25 °C (kPa)
Methanol 15.8 15 64.55/–97.68 470/15 (open) 16.9

Formic acid 6.3 100 100.56/8.27 520/59 (open) 43.1
Natural gas 8.1 (20 MPa) 2 –161/–183 537/–188 147 (15 °C)
(CH4)
Gasoline 34.5 30 17–220/≤–40 300/≤–43 50–93 (37.8 °C)
Diesel oil 36.3 23 140–400/–29 to 250/40–70 ≤0.35 (37.8 °C)
–18
Hydrogen 5.1 (70 MPa) 120 –252.87/–259.14 500–571/— 1.65 × 105
1.3 Application and Market Studies of CO2 Hydrogenation Products 5
Others
11%
Formaldehyde
26%
MTO
23%
Acetic
Acid
8%
Alternative MTBE
Fuels 12%
20%
Figure 1.3 Global methanol demand in 2018. Source: Data from Global methanol demand
(Methanol Institute) [16].
established process consumes 37.5 GJ of natural gas and emits 1.49 ton of CO2 [18]. In 2018,
the global production of methanol was approximately 91.7 Mton, and since 2015, its pro-
duction has grown by approximately 16% [16]. Approximately 26% and 8% of the methanol
produced worldwide is consumed to produce formaldehyde and acetic acid, respectively, as
the conventional demands. Methanol can be used as a fuel for internal combustion engines
and fuel cells because it has a comparably high-octane number of 113 and a density approx-
imately half that of gasoline. In addition, methanol can be transformed into gasoline
through the methanol-to-gasoline (MTG) process developed by Mobil in the 1970s [19].
Another growing market for methanol is the production of light olefins (i.e. ethylene
(152 Mton yr−1) and propylene (103 Mton yr−1) in 2017), [20] which are monomer feed-
stocks for polyethylene and polypropylene as basic products of the plastics industry [21].
The concept of a so-called methanol economy was independently proposed by Olah and
Asinger due to the chemical’s promising characteristics for use as an energy vector and
chemical feedstock [22–24]. Therefore, the production of methanol by CO2 conversion is
regarded as an attractive and potentially profitable route for CO2 utilization.
1.3.3 Methanation
CO2 methanation, also known as the Sabatier process, affords methane by the exothermic
reaction of CO2 with H2. The commercial methanation of CO2 is performed at 300–550 °C
and above 5 bar. Most CO2 methanation processes are considered to be a linear combina-
tion of rWGS and CO methanation. The process is expected to be a power-to-gas concept
for converting renewable electrical energy into methane as chemical energy. In other
words, the main goal of methanation is the intermediate storage of renewable electricity in
methane as an energy carrier. Since fossil-based natural gas is a common fuel, there would
be easy access to existing infrastructure.
Due to the significant interest in CO2 methanation, the first pilot plant capable of pro-
ducing 0.5 Nm3 h−1 of synthetic natural gas was built in Japan [25]. In terms of commercial
6 1 Introduction
installations, Audi has an operational CO2 methanation facility (max. 325 Nm3 h−1) using
renewable H2 (max. 1300 Nm3 h−1) from electrolysis (max. 6.0 MW) in Germany [26, 27].
1.3.4 Energy Storage

The two most growing renewable energy sources, solar and wind, are intermittent and thus
provide highly fluctuating electrical energy. In addition, the region’s best suited areas for
the production of renewable energy are often far from consumption areas, i.e. cities. These
cause the two key problems of storage and transport. Certainly, electrical energy is an effec-
tive way to transfer energy within 1000 km and can be stored in batteries. However, low-
cost solutions for the large-scale storage and long-range transport of electrical energy must
be developed to improve energy security and balance energy prices.
The transformation of excess renewable energy into chemical energy by converting CO2
is one promising option. CO2-based compounds, such as methane, methanol and formic
acid, can store energy as gas or liquids with comparably high-energy densities. Especially
liquids can be easily transported and release energy as H2 or electricity through oxidation
and fuel cells when there is a greater demand. In other words, CO2 can act as an energy
vector between electrical and chemical energy. Recently, the electroreduction of CO2 to
chemical fuels has been receiving increasing attention because it allows for the direct use
of renewable electricity without conversion to high-cost H2 by water electrolysis (see
Chapter 9). Much more CO2 is in demand as a feedstock for fuels than for chemicals and
mineralization. In addition, related photo-catalytic processes gain more and more interest.
1.4 Supply of Materials
The CO2 hydrogenation approach requires H2, CO2, and an energy supply. In particular,
how much the energy-intensive hydrogenation process contributes to mitigating CO2 emis-
sions will be dominated by the H2 source. Obviously, H2 must be produced with the help of
a renewable electricity source such as water electrolysis and not from fossil fuels.
1.4.1 CO2 Supply

Capture, purification, and transport of CO2 are essential for its utilization. Table 1.3 lists
several large CO2 sources with their typical amounts and concentrations of CO2 as well as
impurities. In present CO2 merchant market (approximately 230 Mton, US$7.7 billion), the
fermentation process (i.e. bioethanol production) and ammonia production, which provide
close to 100% CO2, are predominantly CO2 sources [5, 30]. The CO2 generated from ethanol
fermentation commercially supplies roughly 270 000 ton of CO2 annually for EOR through
pipeline from Kansas to Texas [28]. On the other hand, the production of electricity and
heat accounts for 41% of global CO2 emissions (Figure 1.4), and the transport and indus-
trial sectors account for an additional 25% and 19%, respectively [32]. However, suitable
sources of CO2 for use in chemical transformation are limited. The gases contain various
impurities, the separation of which is both energy and cost intensive. To supply CO2 of an
1.4 Supply of Material 7
Table 1.3 Concentration of CO2 and contaminants from various sources.
Source Amount/Mton CO2 concentration/% Impurities
Ethanol fermentation [28, 30] 50 99 EtOH, MeOH, H2O, H2S

Anhydrous ammonia 30 >95 NH3, CO, H2, H2O
Natural deposits 13 90–100 N2, O2, He
Power plants 4287 10–15 N2, H2O, SOx, NOx, CO
Steelmaking 266 18–20 N2, SOx, NOx, O2
Cement production [31] 220 14–33 SOx, NOx, O2
Atmosphere 3 200 000 0.04 N2, O2, SOx, NOx
Source: Carbon Recycling International; Capturing and Utilizing CO2 from Ethanol: Adding Economic
Value and Jobs to Rural Economies and Communities While Reducing Emissions (2017); and
Greenhouse Gas Inventory Data [9, 28, 29].
Other
4%
Residential
6%
Electricity and
Transport heat producers
25% 41%
Other
energy
Industry industries
19% 5%
Figure 1.4 CO2 emissions from fuel combustion. Source: Data from IEA, CO2 emissions from fuel
combustion, 2020 [32].
appropriate quality for use in chemical conversion processes, capture and separation are
required (Table 1.4) [33]. The most effective CO2 capture method as the current industrial
standard is chemical absorption in an aqueous solution of an amine-based organic com-
pound. However, the cost (35 US$/ton) and energy consumption (2.5 GJ ton−1) of amine
capture must still be reduced to provide economically viable routes from carbon dioxide to
fuels [34, 35].
Recently, the direct capture of CO2 from ambient air, called direct air capture (DAC), has
received increasing attention [36]. One of the advantages of DAC is that it can be located
anywhere, because it is unnecessary for CO2 transport. However, from both engineering
and chemistry views, there remains much room for improvements to the sorbents and pro-
cesses. Additionally, thorough techno-economic analyses of DAC processes are neces-
sary [37].
8 1 Introduction
Table 1.4 CO2 capture technologies.
Capture technology Technical principle
Chemical absorption Chemical reaction between CO2 and absorbent by a temperature swing.
Physical absorption Dissolution of CO2 into a liquid, the efficiency of which depends on the
solubility of CO2 in the liquid.
Solid absorption Absorption into solid absorbents, which include porous materials
impregnated with amines for low-temperature separation or other solid
absorbents for high-temperature separation.
Physical adsorption Adsorption onto porous solids such as zeolites by a pressure or
temperature swing.
Membrane Permeation through a membrane with selective permeability for different
separation gas species.
Source: Based on Styring [33].
2000
Biofuels Geothermal
Hydro Wind
1500
Solar PV Solar thermal
Tide, wave, ocean
TWh
1000
500
0
Ca il
na
SA
da
ly
K
a
az
wa
an
di
pa
si
U
Ita
hi
na
us
U
In
Br
Ja
or
C
R
er
N
G
Figure 1.5 Low-carbon electricity generation by source in 2017. Source: Data from explore energy
data by category, indicator, country or region (IEA) [38].
1.4.2 Energy and H2 Supply

Another consideration is the energy required to capture and convert CO2, which must cer-
tainly be derived from renewable sources (Figure 1.5) [38]. If this energy comes from fossil
oils, much more CO2 will be emitted than separated. Fortunately, the renewables now
account for over 25% of global power output (hydro: 16%, wind: 5%, PV: 2%), [1] and the
costs of PV and wind power become even lower than that of fossil fuels (natural gas and
coal) (Figure 1.6) [39]. Thus, electricity from renewable sources can be converted into H2
by water electrolysis, which can be performed on an industrial scale. Nevertheless, H2 pro-
duced by electrolysis systems (2.5–6 US$/kgH2) is at present more expensive than that from
1.6 Conclusion and Perspective 9
40
Nuclear Coal
30 Natural Gas Solar PV
Wind
/KWh
20
10
0
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Year
Figure 1.6 Levelized cost of energy comparison: Renewable energy versus conventional
generation. Source: Data from Lazard.com, Lazard’s levelized cost of energy analysis [39].
current industrial production based on conventional fossil sources, like natural gas reform-
ing and coal gasification (<1 US$/kg H2) [40, 41].
1.5 Political Aspect: Tax
The future prospects for CO2 utilization on large scale will mainly depend on policy sup-
port. The carbon tax, a fee imposed on the burning of carbon-based fuels (coal, oil, gaso-
line, and natural gas), is one policy for reducing the use of fossil fuels. To reduce CO2
emissions, as many as 29 countries have implemented carbon taxes as of 2019. Tax rates,
including energy taxes, differed according to use and fuel type in 2017. For example, high
tax rates are imposed on gasoline in every country, from yiSOLL in the United States to
yiSOLL - yiIST in the Netherlands [42]. On the other hand, there are also significant differ-
ences in tax rates for the industrial sector depending on the country (Figure 1.7). An
increasing of the tax rates of carbon-based fuels seems to be necessary to motivate our
societies to switch to clean energy.
1.6 Conclusion and Perspectives
CO2 utilization will play a crucial role in achieving the internationally agreed climate and
energy goals. In particular, the conversion of CO2 to fuels and chemicals will be of signifi-
cant importance. However, these technologies are still in their infancy, and the following
issues require consideration and technological improvements:
(i) Supply of H2 and power from renewables.

(ii) Cost reduction, mainly for the supply of low-carbon H2.
(iii) Political support to shift from a fossil-based to CO2-based economy.
(iv) Highly efficient catalysts to minimize energy usage for the valorization of CO2.
10 1 Introduction
200
Heavy oil (industrial)
150 Coal (industrial)

Natural gas (industrial)
$/ton of CO2
100
50
lia
SA
ce
en
nd
n
an
nd
ar
ad
pa
U
ra
an
ed
la
U
m
m
rla
n
Ja
st
er
Fr
Sw
Ca
en
er
Au
he
itz
G
D
Sw
et
N
Figure 1.7 Carbon tax rate per ton of emitted CO2. Source: Data from the Ministry of the
Environment of Japan [42].
In addition, critical evaluation from an LCA perspective will be necessary.

In any case, the spread and expansion of renewable energy are essential, which, in turn,
require energy storage and transport. CO2-based fuels produced by CO2 hydrogenation will
contribute to these needs. Therefore, further research into CO2 hydrogenation is necessary
from a standpoint of both fundamental science and application. In this respect, we believe
the focus of this book on the hydrogenation/electroreduction of CO2 to formic acid and
methanol as chemicals and fuels using homogeneous and heterogeneous catalysts will be
of interest to many scientists. It will serve as motivation for studying the development of
catalysts for the hydrogenation of CO2 as a fuel and bulk chemical. In addition, the chal-
lenge of activating unreactive CO2 will stimulate the curiosity and creativity of chemists.
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13
Homogeneously Catalyzed CO2 Hydrogenation to Formic

Acid/Formate by Using Precious Metal Catalysts
Wan-Hui Wang1,2, Xiujuan Feng1 and Ming Bao1,2
1
Dalian University of Technology, State Key Laboratory of Fine Chemicals, 2 Linggong Road, Ganjingzi District, Dalian,
116023, China
2
Dalian University of Technology, School of Chemical Engineering, 2 Dagong Road, Liaodongwan New District, Panjin,
124221, China
2.1 Introduction
CO2 hydrogenation to formic acid (FA)/formate has a long history, and heterogeneous
catalytic transformation even dates back to 1914 [1]. Inoue et al. in 1976 reported CO2
hydrogenation by using Ru-, Rh-, and Ir-based complexes and has paved the way for the
homogeneous catalytic hydrogenation of CO2 [2]. Considering that CO2 emission has
increased significantly and causes severe environmental problems, CO2 fixation and utili-
zation have attracted attention in the last three decades [3], and CO2 hydrogenation to FA
or formate has been revived. Considerable efforts have been devoted to this transformation,
and a remarkable progress has been achieved.
Developing highly efficient complexes requires modulation of the electronic and steric
environments of the metal center. Adjusting the ligands and/or metals generates effective
complexes for the catalysis of certain reactions. Phosphorous ligands had been widely used
to develop catalysts during the initial CO2 hydrogenation research. C,N- and N,N-chelated
ligands, N-heterocyclic carbene (NHC) ligands, and pincer ligands have also been recently
developed. Among these ligands, functionalized N,N-ligands and non-innocent pincer
ligands effectively promote the catalytic activity of the complexes and usually contain tau-
tomerizable moieties, including pyridinol, imidazole or imidazoline, amide, and alkyl pyri-
dine as shown in Scheme 2.1. Tautomerizable ligands can transfer electrons coupled with
proton migration. The acidity of the active protons increases when these ligands coordinate
with the metal center by donating electrons. At a certain pH, the active proton can be
abstracted by a base. Therefore, the complexes, especially those bearing OH or NH groups,
show proton-responsive property. Deprotonation also strengthens electron-donating abil-
ity of the ligands and facilitates electron transfer from ligand to metal. Additional func-
tions, such as acting as a pendant base, are gained in some cases. These unique properties
CO2 Hydrogenation Catalysis, First Edition. Edited by Yuichiro Himeda.

© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
14 2 Homogeneously Catalyzed CO2 Hydrogenation to Formic Acid/Formate
OH O
R1 R1
R N R N
N N H
H
H
N N O OH
R2 R2
N N R1 N R1 N
H H
Scheme 2.1 Tautomerizable ligands for functional complexes.
of tautomerizable ligands endow complexes with versatility for catalytic hydrogenation. In

this chapter, the important role of ligands, especially tautomerizable ligands, is presented.
CO2 hydrogenation is commonly promoted using inorganic or organic base, and further
acidification is required to obtain pure FA. The direct hydrogenation of CO2 to FA under
base-free conditions has recently been achieved albeit with a relatively low activity. Process
design and development enable the production of pure FA and the recycling of homogene-
ous catalysts. The important progresses in catalyst activity, reaction mechanism, and
process development are discussed herein.
CO2 hydrogenation is a popular topic well reviewed by Leitner, Jessop, Himeda, Beller,
and Ding et al. [4]. Although remarkable progress in CO2 reduction to FA/formate using
hydrogen sources, such as alcohols, boranes, and silanes, has been reported [5], we focus
on the recent advances in the homogeneous hydrogenation of CO2 to FA/formate catalyzed
by noble metal–based complexes using molecular hydrogen. In this chapter, we briefly
introduce previous studies and mainly focus on the progress in last decades. Table 2.1 lists
the selected catalytic systems for CO2 hydrogenation with precious metals. Notably, CO2
and bicarbonate can serve as hydrogenation substrates alone or in combination with others.
State-of-the-art homogeneous CO2 hydrogenation to FA/formate catalyzed by precious
metals is introduced in this chapter.
2.2 Ir Complexes
Among the commonly used precious metal–based catalysts, Ir catalysts exhibit high activ-
ity for CO2 hydrogenation. Ir complexes with functionalized ligands show remarkable cata-
lytic activity. This section covers the development of different types of ligands, especially
tautomerizable ligands (i.e. pyridinol, diazole, amide, and pincer ligands) for highly effi-
cient Ir complexes.
2.2.1 Ir Complexes with N,N-ligands

2.2.1.1 Tautomerizable N,N-ligands with OH Groups
Himeda et al. reported half-sandwich Ir complexes with N,N-ligand-bearing OH functional
groups, including 4DHBP (4,4′-dihydroxy-2,2′-bipyridine) [47] and DHPT (4,7-dihydroxy-
1,10-phenanthroline) [48] for CO2 hydrogenation. These complexes exhibit high activity
OH
OH OH HO
N N N N N N
OH
OH
N N N N N N
OH OH HO
OH
bpy 4DHBP DHPT 6DHBP 5DHBP 3DHBP
Figure 2.1 Proton-responsive ligands used for CO2 hydrogenation.
for CO2 hydrogenation to formate in aqueous solution. Following these studies, nDHBP
(n,n′-dihydroxy-2,2′-bipyridine, n = 3, 4, 5, 6) (Figure 2.1) [9, 49] and other related N,N-
ligand-bearing OH groups (Figure 2.3) have also been developed by Himeda group. The
relationship between the structure and catalytic activity of the corresponding complexes
was investigated systematically in CO2 hydrogenation. The features and merits of the func-
tional ligands are presented as follows.
Electronic Effects Electron-donor ligands are favorable in enhancing the catalytic activity
of complexes in CO2 hydrogenation [23, 50]. To illustrate the electronic effect of ligands on
complex catalytic activity, Himeda et al. developed a series of half-sandwich Ir complexes
[Cp*Ir(4,4′-R2-bpy)Cl]+ (Cp*: pentamethylcyclopentadienyl, R = OH, OMe, Me, H) with
different electron-donating groups [10, 47, 48, 51]. In Figure 2.2, Hammett plot shows the
linear correlation between the initial turnover frequencies (TOFs) and σp+ values of the
substituents in the [Cp*Ir(4,4′-R2-bpy)(OH2)]SO4 complexes. Among the complexes
examined, complex [Cp*Ir(4DHBP)(OH2)]SO4 showed the highest TOF because OH is the
strongest electron donor among the four substituents (i.e. OH, MeO, Me, and H). The
electronic effects of complexes [Cp*Ir(6,6′-R2-bpy)(OH2)]SO4 (R = OH, OMe, Me, H) with
substituents at 6,6′-position were also studied (Figure 2.2) [9]. A similar tendency to
4,4′-substituted analogs was observed. Thus, strong electron-donating substituents are
responsible for the high catalytic activity of complexes with OH.
The pyridinol ligand could deprotonate under basic conditions to generate oxyanion
form that could be protonated under acidic conditions to regenerate pyridinol. Therefore,
the corresponding complexes with hydroxy-substituted ligands are proton-responsive [52].
This functional complex has the advantage of tunable polarity and water solubility depend-
ing on the solution pH. The solubility of proton-responsive complexes is altered because
the pH of the reaction solution changes during the reaction, and an efficient catalyst recy-
cling of homogeneous [Cp*Ir(DHPT)Cl]Cl is consequently achieved [48b]. Another merit
is the tunable electron-donating ability. The pKa values of the OH groups of the complexes
were determined using UV–vis spectrophotometric titration and are listed in Table 2.2. The
OH groups in the complexes are acidic (pKa: 4–5). The reaction solution is aqueous bicar-
bonate, which is basic (pH: ~8). Therefore, the OH groups in the complex are deprotonated
to the oxyanion forms under the reaction conditions (Scheme 2.2). Oxyanion (σp+ = −2.30)
is a remarkably stronger electron donor than OH group (σp+ = −0.92) [47]. Hence, the
electron-donating ability of the functional ligand is enhanced in basic solutions.
2.2 Ir Complexe 27
3 a
b
–
2 O
log(kR/kH)
Me
1
H
MeO
0
–2.5 –2 –1.5 –1 –0.5 0 0.5

σp+
Figure 2.2 Correlation between initial TOFs and σp+ values of substituents (R) for the CO2
hydrogenation catalyzed by (a) [Cp*Ir(4,4′-R2-bpy)(OH2)]SO4 (R = OH, OMe, Me, H; triangles) and (b)
[Cp*Ir(6,6′-R2-bpy)(OH2)]SO4 (R = OH, OMe, Me, H; circles). Reaction conditions: 1 MPa of H2/CO2
(1/1), 80 °C; (a) 0.02–0.2 mM catalyst in 1-M KOH and (b) 0.01–0.2 mM catalyst in 1-M NaHCO3.
Source: From Wang et al. [9], © 2012 Royal Society of Chemistry. Reprinted with permission of Royal
Society of Chemistry.
Table 2.2 pKa values of functional OH groups in complexes.
Complex pKa of OH References
[Cp*Ir(4DHBP)(OH2)]SO4 5.2 [49]

[Cp*Ir(4DHBP)(OH2)]SO4 5.0 [9]
[Cp*Ir(5DHBP)(OH2)]SO4 5.6 [49]
[Cp*Ir(6DHBP)(OH2)]SO4 4.7 [49]
[Cp*Ir(6DHBP)(OH2)]SO4 4.1 [9]
[Cp*Ir(N3)(OH2)]SO4 3.9 [13]
[(Cp*IrCl)2(N1)]Cl2 3.8 [11]
[Cp*Ir(N6)(OH2)]SO4 4.0 [53]
Tautomerism between the oxyanion and the ketone forms is confirmed via the structural
analysis of deprotonated complexes [49]. In accordance with the data from X-ray structural
analysis, the C─O bond lengths in [Cp*Ir(4DHBP)(OH2)]2(SO4)2(H2O)5 are 1.329(3) Å. By
contrast, those C─O bond lengths in the deprotonated [Cp*Ir(4DHBP−2H+)(OH2)](H2O)4
are 1.295(4) Å. The short C─O bond lengths in the latter case imply the double-bond char-
acter of C─O− bond in the doubly deprotonated 4DHBP ligand of the complex. The C─O
bond lengths in [Cp*Ir(6DHBP)(OH2)]2(SO4)2(H2O)9 are 1.319(3) and 1.321(3) Å, whereas
those in deprotonated [(Cp*Ir(6DHBP−2H+)(OH2)](H2O)2 are as short as 1.272(9) Å. Thus,
OH group deprotonation shortens the C─O bond lengths sufficiently for a C═O bond.
Pyridinol deprotonation results in a pyridinone tautomer via conjugation (Scheme 2.2).
The TOF of [Cp*Ir(4DHBP)(OH2)]SO4 is 1000 times higher than that of [Cp*Ir(bpy)
(OH2)]SO4 under the same conditions (i.e. 1 MPa CO2/H2 (1/1), 80 °C). Therefore, deproto-
nation and tautomerism contribute to the high electron-donating capacity of the ligand
and considerably improve its catalytic activity.
Pendant-Base Effects As shown in Figure 2.2, the activity of [Cp*Ir(6DHBP)(OH2)]2+

(TOF: 8050 h ) is markedly higher than that of [Cp*Ir(4DHBP)(OH2)]2+ (TOF: 5100 h−1)
−1
under the same conditions (1 MPa of H2/CO2 (1/1), 80 °C). Given the similar electronic
effect of hydroxy groups at the para and ortho positions, catalytic activity enhancement is
attributed to the position effect of the OH groups in 6DHBP. Experimental and computational
studies were conducted to investigate the effects of adjacent OH [9, 12, 49].
Catalytic CO2 hydrogenation usually follows three steps: heterolytic cleavage of H2 to gen-
erate metal hydride, CO2 insertion into the metal hydride to yield formato intermediate and
formate dissociation. Nuclear magnetic resonance (NMR) experiments with D2O/KOD solu-
tion [Cp*Ir(6DHBP)(OH2)]2+ and [Cp*Ir(4DHBP)(OH2)]2+ in the H2 atmosphere suggested
that [Cp*IrH(6DHBP)(OH2)]2+ formation is faster than that of [Cp*IrH(4DHBP)(OH2)]2+. In
addition, 95% of [Cp*Ir(6DHBP)(OH2)]2+ is converted to [Cp*IrH(6DHBP)(OH2)]2+ after
0.5 hour in 0.2 MPa H2. By contrast, only 90% of [Cp*Ir(4DHBP)(OH2)]2+ is transformed to
[Cp*IrH(4DHBP)(OH2)]2+ after 40 hours in 0.5-MPa H2. Density functional theory (DFT) cal-
culations with complex [Cp*Ir(6DHBP)(OH2)]2+ indicated that the heterolytic cleavage of H2
is a rate-determining step under basic conditions (pH 8.3) [9]. A study on deuterium kinetic
isotope effect further indicated that water molecule is involved in the rate-limiting heterolysis
of H2 for complexes with pendant OH groups [12]. Moreover, DFT calculations showed that
the oxyanions at the 6,6′-position of 6DHBP act as pendant bases and assist in H2 heterolysis
via a proton relay with the participation of a H2O molecule (Scheme 2.3) [54]. The
OH n O n 2 O n 2
N 2H+ N N
M M M
+2H+
N N N
OH O O
Scheme 2.2 Acid–base equilibrium between hydroxy and oxyanion forms and resonance
structures of oxyanion form.
PT
0 0 0
O O H H O H H
O
N H2 N PT N H O
H H
Ir Ir H Ir
H2O
N N N
Cp* Cp* Cp*
O O O
Scheme 2.3 Proposed mechanism for H2 heterolysis assisted by the pendant base and a water
molecule through proton relay. PT indicates proton transfer. Source: From Wang et al. [12], © 2013
American Chemical Society. Reprinted with permission of American Chemical Society.
2.2 Ir Complexe 29
pendant-base effect of OH groups is similar to that of Fe-guanylpyridinol cofactor in [Fe]-

hydrogenase [55]. These findings revealed the crucial effect of pendant oxyanion in H2 heter-
olysis and provided a novel strategy in designing highly efficient catalysts for CO2
hydrogenation.
Combination of Electron-donating Effect and Pendant-base Effects The high activity of

[Cp*Ir(6DHBP)(OH2)]2+ complex is attributed to the functional ligands, which combine
electron-donating and pendant-base effects. The same strategy is applied to develop other
highly efficient complexes, including [(Cp*IrCl)2(N1)]2+ and [Cp*Ir(Nn)(OH2)]2+ (n = 1–6,
Figure 2.3). Dinuclear complex [(Cp*IrCl)2(N1)]2+ (N1 = 4,4′,6,6′-tetrahydroxy-2,2′-
bipyrimidine) provides an extraordinary TOF of 64 h−1 and turnover number (TON) of
7200 for 336 hours under ambient conditions (0.1 MPa H2/CO2 (1/1), 25 °C) in CO2
hydrogenation [11]. [Cp*Ir(N2)(OH2)]2+ (N2 = 2,2′,6,6′-tetrahydroxy-4,4′-bipyrimidine)
bears four pendant OH groups and shows comparable activity with a TOF of 66 h−1 under
the same conditions [12]. The markedly high TOFs and TONs achieved by [Cp*Ir(Nn)
(OH2)]2+ and [Cp*Ir(N2)(OH2)]2+ under elevated conditions are shown in Table 2.1. Their
similar catalytic activities indicated that the electron-donating effect of the ligand is more
important than the number of metal centers.
The five-membered N-heterocycle is more electron rich than the pyridine cycle because
the former contains six π-electrons but only five atoms in the ring. The electronic effects of
ligands were explored by Himeda and coworkers by developing functional complexes with
N3–N5 that contain OH–substituted pyridine or pyrimidine and one pyrazole cycle [13,
56]. However, the catalytic activity of these complexes was lower than that of [Cp*Ir(4DHBP)
(OH2)]2+. [Cp*Ir(N3)(OH2)]2+, [Cp*Ir(N4)(OH2)]2+, and [Cp*Ir(N5)(OH2)]2+ provided
TONs of 388, 440, and 610, respectively, after one hour in 2 M KHCO3 at 1 MPa H2/CO2
(1/1) and 50 °C. By contrast, [Cp*Ir(4DHBP)(OH2)]2+ afforded a TON of 650 under the
same conditions [49]. Complexes with pyrimidine ligands bearing two OH groups (i.e. N4
and N5) provided higher TONs than that with pyridine ligand bearing one OH (N3). The N
position in pyrimidine also affects the catalytic activity.
Introducing OH substituents on the ligand is limited to six-membered rings, such as
pyridine or pyrimidine. Himeda and coworkers recently developed a half-sandwich Cp*Ir
complex with a new ligand N6 comprising a pyridyl pyrazole with an OH group on the
pyrazole moiety for CO2 hydrogenation [53]. UV–vis spectrophotometric titration indi-
cated that pKa of the OH is 4.0 (Table 2.2). Under basic reaction conditions, the OH group
is readily deprotonated to an oxyanion, which is a stronger electron donor than the OH
group as aforementioned. Therefore, oxyanion could increase the electron density on the
HO N OH HO HO
HO OH HO N OH HO OH
N N N N N N N N
N
N N N
N N N N N N N
HO OH HO N OH
N1 N2 N3 N4 N5 N6
Figure 2.3 Proton-responsive N,N-ligands with pendant OH groups.

Ir center and improve the catalytic activity. Under ambient conditions (i.e. 25 °C, 0.1 MPa
H2/CO2 (1/1)), [Cp*Ir(N6)(OH2)]2+ provides a high TOF of 34 h−1 and a TON of 1250 after
140 hours. Thus, [Cp*Ir(N6)(OH2)]2+ is more active than [Cp*Ir(6DHBP)(OH2)]2+ and
[Cp*Ir(N4)(OH2)]2+ with a TOF of 27 and 11 h−1, respectively, under the same conditions.
Introducing the OH group on a pyrazole ring can also improve the robustness of the
catalyst.
2.2.1.2 N,N-ligands with NH Group

In addition to the electron-rich property of the diazole cycle, the NH moieties in diazole
rings might be deprotonated and provide similar merits to pyridinol. Wang and Himeda
and coworkers developed Ir complexes with electron-donating N,N-ligands N7–N11 bear-
ing NH groups (Figure 2.4) [19, 57]. Although complexes [Cp*Ir(Nn)(OH2)]SO4 (n = 7–11)
are not effective for CO2 hydrogenation, two of them, [Cp*Ir(Nn)(OH2)]SO4 (n = 7, 8) with
2,2′-biimidazole (N7) and 4,4′,5,5′-tetramethyl-2,2′-biimidazole (N8) ligands, are highly
active for FA dehydrogenation [57].
According to the pKa of NH (Table 2.3), the NH in imidazole and pyrazole is prone to
deprotonation under reaction conditions (pH ~8.5), resulting in resonance and causing
electrons to be donated to the Ir center (Scheme 2.4). Introducing Me group to NH prevents
deprotonation and blocks electron donation. Comparison of the catalytic activity between
complexes [Cp*Ir(Nn)Cl]Cl (n = 9, 10) with NH groups and [Cp*Ir(Nn)Cl]Cl (n = 12, 13)
with NMe groups indicated that NH deprotonation promotes the catalytic activity
(Table 2.4, entry 1 versus 3 and entry 2 versus 4).
Changing the imidazole cycle to imidazoline (N15 versus N10) considerably improves
the catalytic activity and doubles the TOF (Table 2.4, entry 2 versus 5). The TOF of the
complex [Cp*Ir(N15)(OH2)]2+ with imidazoline moiety is almost the same as that of
[Cp*Ir(N16)(OH2)]2+ with N-methylated imidazoline moiety (Table 2.4, entry 5
N
N NH N NH N
N N
N NH
N NH N NH N
N HN N
N
NH
N7 N8 N9 N10 N11 N12
N NH
N N N HN N HN N
N NH
N N HN N N N HN N HN N
N13 N14 N15 N16 N17 N18
Figure 2.4 Selected N,N-ligands with NH groups for CO2 hydrogenation.

2.2 Ir Complexe 31
Table 2.3 pKa values of functional NH groups in complexes.
Complex pKa of NH References
[Cp*Ir(N9)Cl]Cl 6.3 [19]

[Cp*Ir(N10)Cl]Cl 6.4 [19]
[Cp*Ir(N8)(OH2)]SO4 8.8 [57]
[Cp*Ir(N17)(OH2)]SO4 8.9 [58]
[Cp*Ir(N17)Cl]Cl 9.0 [59]
versus 6) [58]. As such, NH in imidazoline moiety is not deprotonated, and the electron-
donating ability under the reaction conditions is improved. Nevertheless, the imidazoline
cycle remarkably enhances the catalytic activity. The ligand was further modified by
replacing the pyridine cycle with another imidazoline, i.e. 2,2′-biimidazoline (N17). The
catalytic activity of [Cp*Ir(N17)(OH2)]2+ for CO2 hydrogenation is remarkably enhanced.
A high TOF of 1290 h−1 is achieved at 50 °C and 1.0 MPa H2/CO2 (1/1). By contrast, a low
TOF of 20 h−1 is obtained by 2,2′-biimidazole complex [Cp*Ir(N7)(OH2)]2+ under the
same conditions. In addition, the 2,2′-biimidazoline-based complex [Cp*Ir(N17)(OH2)]2+
provides a high TOF of 43 h−1 under ambient conditions. The pKa of NH (Table 2.3) sug-
gests that the NH moieties in imidazoline of complex [Cp*Ir(N17)(OH2)]2+ are less likely
to deprotonate under reaction conditions (pH ~8.5), and this high activity is attributed to
the resonance structure of amidine. The π electrons in aromatic imidazole are delocalized
to the whole cycle of five atoms via resonance, whereas the amidine moiety in nonaro-
matic imidazoline holds concentrated electrons on N and donates a high number of elec-
trons to the Ir center. Consequently, an activity higher than that for the aromatic imidazole
catalyst is observed.
In 2016, Li and coworkers reported that complexes [Cp*Ir(Nn)Cl]Cl (n = 17, 18,
Figure 2.4) are highly efficient catalysts for CO2 hydrogenation in water under base-free
conditions [60]. A high TOF of 13 109 h−1 and a TON of 10 000 were achieved with
[Cp*Ir(N18)Cl]Cl at 80 °C and 5 MPa H2/CO2 (1/1). This is the highest activity yet reported
for CO2 hydrogenation under base-free conditions. In the presence of a base, the high activ-
ity of [Cp*Ir(N18)Cl]Cl is comparable with that of a highly efficient complex
[(Cp*IrCl)2(N1)]2+. A high TON of 196 000 was obtained for 24 hours at 80 °C and 5 MPa
H2/CO2 (1/1) in 2 M KHCO3.
Yoon and coworkers recently synthesized a half-sandwich Ir complex [Cp*Ir(N14)Cl]Cl
containing bibenzimidazole as a proton-responsive N-donor ligand [18]. Deprotonation of
one NH was observed in the NMR test with the complex in the presence of Et3N. [Cp*Ir(N14)
Cl]Cl showed a TON of 100 at the initial one hour under 4 MPa H2/CO2 (1/1) at
50 °C. Although the catalytic activity is low, the TON value is 20 times higher than that of
[Cp*Ir(bpy)Cl]Cl under the same reaction conditions. The authors supposed that the
deprotonation of bibenzimidazole ligand and the electron-donating effect of generated N−
enhance the catalytic activity compared with that of [Cp*Ir(bpy)Cl]Cl. The low activity is
attributed to the structural instability of the catalyst from the steric repulsion between
bibenzimidazole and Cp* ligands.
N –H+ N N
M M M
HN N N N N N
Scheme 2.4 Deprotonation and resonance of N,N-ligands with NH groups in complex.
Table 2.4 Catalytic performance of complexes with NH and NMe moieties.a
Entry Complex Initial TOFb/h−1 TON for 24 hours References
1 [Cp*Ir(N9)Cl]Cl 390 4600 [19]

2 [Cp*Ir(N10)Cl]Cl 83 1300 [19]
3 [Cp*Ir(N12)Cl]Cl 17 — [19]
4 [Cp*Ir(N13)Cl]Cl 20 — [19]
5 [Cp*Ir(N15)(OH2)]SO4 168 — [58]
6 [Cp*Ir(N16)(OH2)]SO4 181 — [58]
a
Performed in 10 mL of a 2-M KHCO3 aqueous solution (pH 8.5) at 50 °C under 1.0 MPa H2/CO2 (1/1) with
catalyst loading of 20 μM.
b
Initial TOF was determined in the first hour.
2.2.1.3 Tautomerizable N,N-ligands with OH and NH Groups

Complex [Cp*Ir(N19)(OH2)]2+ with a pyrimidinyl imidazoline ligand-bearing two OH
groups was initially employed for the highly efficient FA dehydrogenation [56] and was then
used in CO2 hydrogenation together with the OH-substituted pyridinyl imidazoline analogs
[Cp*Ir(Nn)(OH2)]2+ (n = 20–22, Figure 2.5) [61]. The catalytic activities of these complexes
were examined at 50 °C and 1 MPa H2/CO2 (1/1) in 2 M K2CO3. [Cp*Ir(N19)(OH2)]2+ gave a
high TOF of 1500 h−1 for the initial one hour. [Cp*Ir(N20)(OH2)]2+ (TOF: 1090 h−1) with OH
at the para position of pyridine cycle showed lower activity than [Cp*Ir(N21)(OH2)]2+
(TOF: 1600 h−1) with OH at the ortho position. Hence, the pendant-base effect improves the
catalytic activity. [Cp*Ir(N22)(OH2)]2+ with two OH-substituted pyridinyl imidazoline
afforded a considerably high initial TOF of 2600 h−1 under the same conditions. The activi-
ties of [Cp*Ir(N19)(OH2)]2+ and [Cp*Ir(N22)(OH2)]2+ were compared, and an additional
electronegative N in ligand was seemingly unfavorable to its electron-donating effect. In
addition, unprecedented TOF of 106 h−1 and TON of 7280 in 336 hours were achieved using
[Cp*Ir(N22)(OH2)]2+ at 25 °C and 0.1 MPa H2/CO2 (1/1). The high efficiency of [Cp*Ir(N22)
(OH2)]2+ is attributed to the combination of the strong electron-donating effect and the pen-
dant-base effect from the OH-substituted pyridinyl imidazoline.
In 2017, Himeda and coworkers prepared a series of complexes [Cp*Ir(Nn)Cl]Cl
(n = 23–25) with a N,N-bidentate ligand consisting of a OH-substituted pyridine ring and
an electron-rich diazole ring bearing an uncoordinated NH group [19]. These complexes
act as highly efficient catalysts for CO2 hydrogenation in basic aqueous solutions. The pKa
values of OH and NH in the Ir complexes were determined using UV–vis spectrophotomet-
ric titration (Table 2.5). The OH and NH groups on the pyridine and diazole rings
2.2 Ir Complexe 33
HO N OH HO OH HO OH
N N N N
N NH HN N HN N HN N
N19 N20 N21 N22
OH HO
H
N N HO N N
N N OH
N N NH
NH
N23 N24 N25
Figure 2.5 Selected N,N-ligands with OH and NH groups for CO2 hydrogenation.
Table 2.5 pKa values of OH and/or NH groups in functional complexes.
Complex pKa of OH pKa of NH References
[Cp*Ir(N23)Cl]Cl 4.4 7.4 [19]

[Cp*Ir(N24)Cl]Cl 4.2 7.3 [19]
[Cp*Ir(N25)Cl]Cl 2.8 5.0 [19]
deprotonated to generate anionic forms in basic conditions (pH 8.5) for CO2 hydrogenation.
The increased electron donation due to the doubly deprotonated ligand and pendant-base
effects markedly improved the catalytic performance of the Ir complexes. Complexes
[Cp*Ir(N23)Cl]Cl, [Cp*Ir(N24)Cl]Cl, and [Cp*Ir(N25)Cl]Cl provided high initial TOFs of
1300, 1600, and 2000 h–1, respectively, at 50 °C and 1 MPa H2/CO2 (1/1) in a 2-M KHCO3
aqueous solution. Spectroscopic and computational investigations revealed that deproto-
nation changes the electronic properties of the complexes and causes proton relay between
the pendant base and the substrate with or without water, resulting in the high catalytic
performance in basic media.
2.2.1.4 Tautomerizable N,N-ligands with Amide Group

In 2017, Himeda and coworkers developed another type of catalysts with picolinamide
[Cp*Ir(Nn)(OH2)]SO4 (n = 26–29) that showed excellent activity for CO2 hydrogenation in
aqueous solution (Scheme 2.5) [20]. [Cp*Ir(N29)(OH2)]SO4 bearing a 4-hydroxy-
N-methylpicolinamidate ligand achieved an initial TOF of 167 h–1 and a TON of 14 700 after
328 hours, thus producing a 0.64-M formate under ambient conditions (0.1 MPa H2/CO2
(1/1), 25 °C) in 1 M NaHCO3. This outcome replaced the record of CO2 hydrogenation to
formate under ambient conditions in water.
Single-crystal X-ray structural analysis of complex [Cp*Ir(N27)(OH2)]SO4 indicated that
pyridine cycle and amide moiety are coplanar. The proton of amide might have been
–
[Cp*Ir(Nn)(H2O)](SO4) (0.2μ moI)
CO2 + H2 + OH HCOO– + H2O
NaHCO3 (1 M, 10 ml), 50 °C
H2/CO2 = 1/1 (1 MPa)
NH2 HN
NH2 HN N N
N N O O
O O
OH OH
N26 N27 N28 N29
TOF: 1310 h–1 1320 h–1 1940 h–1 2660 h–1
Scheme 2.5 In situ–prepared and isolated picolinamide complexes for CO2 hydrogenation. Source:
Redrawn from Kanega et al. [20].
transferred to SO42−, and the N of amide is sp2 hybridized. The amide moiety is converted
to anionic species via deprotonation. Thus, the amide part functions as an anionic ligand
and a strong electron donator. Two resonance structures existed and stabilize the complex
(Scheme 2.6). The high catalytic activity is attributed to the strong electron donation by the
anionic amide moiety and the phenolic oxyanion functional group. This work provides a
novel design strategy for developing highly active catalysts for CO2 hydrogenation.
Himeda and coworkers applied these picolinamide complexes for the electroreduction of
CO2 to formate in water [62]. The combination of the Pt black electrode and the Ir catalyst
with a picolinamide-type ligand resulted in a high faradaic efficiency of formate (95%) and
a current density (7.2 mA/cm2) with −0.49 V versus SHE at pH 8.3. The high selectivity and
efficiency of this electroreduction system is attributed to the easy generation of the Ir–H
intermediates, which exhibit strong CO2 reduction ability in water.
2.2.2 Ir Complexes with C,N- and C,C-ligands

NHCs are electron rich and usually act as σ-donor ligands. Peris and coworkers investi-
gated a series of water-soluble complexes 1–3 with bis-NHC (Figure 2.6) [14, 63]. Hydroxyl
or sulfonate groups were introduced to the side carbon chains to increase water solubility.
Considering that the bis-NHC ligands can form extremely strong bonds with the metal
centers, the corresponding complexes showed high thermal stability and facilitated the
reaction at high temperatures. Complex 3 achieved a high TON of 190 000 at 200 °C and
6 MPa H2/CO2 (1/1) for 75 hours.
R R
O N O N
M M
N N
Scheme 2.6 Resonance structures of picolinamide complex.

2.2 Ir Complexe 35
Cp* OH Cp*
N N N N
HO
Ir Cl Ir
Cl Cl N PF6
N SO3 I Ir I O 3S
N N
N N K K
N N O O
1 2 3
CO2H HO
N Cp* N
Ir
Cp*
Ir N
N Ir
N Cl
N N
H2O N N
O
O
4 5 6
Figure 2.6 NHC Ir complexes developed by Peris et al. Source: Azua et al. [14] and Sanz
et al. [63].
Pérez-Torrente and co-workers synthesized iridium(III) complex [IrH(cod)

{(MeIm)2CHCOO}]+ (4, MeIm: 3-methylimidazol-2-yliden-1-yl) with a
carboxylate-functionalized bis-NHC ligand [17]. Complex 4 was utilized to catalyze CO2
hydrogenation to formate in water by using Et3N as a base. The TON reached 1550 at 110 °C
and 6 MPa H2/CO2 (2 : 1) for 72 hours.
In 2012, Fukuzumi and coworkers synthesized a C,N-chelated Ir complex 5 bearing a
carboxyl group [15]. Complex 5 is proton responsive because the carboxyl group could
deprotonate easily in an aqueous solution. Complex 5 had a pKa value of 4.0 and provided
a TOF of 6.8 h−1 for CO2 hydrogenation in a 0.1-M K2CO3 solution (pH 8.8) with bubbling
H2/CO2 (1/1, 50 ml/min) under atmospheric pressure at 30 °C. In 2017, Papish and cowork-
ers prepared a new scaffold with an NHC bound to pyridin-2-ol [64]. The corresponding Ir
complex 6 was moderately active for CO2 hydrogenation and gave a TON of 910 after
18 hours in 1 M NaHCO3 at 115 °C and 2 MPa H2/CO2 (1/1).
2.2.3 Ir Complexes with Pincer Ligands

In 2009, Nozaki and coworkers utilized Ir pincer complexes for CO2 hydrogenation and
achieved excellent productivity. The PNP pincer complex 7 (Figure 2.7) showed a high TOF
of 150 000 h−1 at 200 °C and a high TON of 3 500 000 for 48 hours at 120 °C under 8 MPa
H2/CO2 (1/1) in H2O/THF (5/1) by using KOH as a base [6]. The catalytic mechanism using
complex 7 was investigated via DFT calculations [6b, 65]. The rate-determining step of a
possible pathway was determined to be deprotonative dearomatization (Scheme 2.7A,B).
The rearomatization of the pyridine cycle can assist in H2 heterolysis (Scheme 2.7D,E). A
similar behavior of pincer ligand was observed in related complexes [66]. This synergistic
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Fig. 1
Fig. 2
Fig. 3
Fig. 4 Fig. 5
A Light-Weight, Two-Horsepower Motor Installed in a Stanch 18-Foot

Canoe will Increase the Range and Utility of Such a Craft; the
Construction Shown Is Simple and within the Capabilities of a Careful
Novice of Fair Mechanical Skill. A View of the Stern from Above is Shown
in Fig. 1. The Engine is Shown Mounted on the Engine Bed, and near the
Stern the Shaft Block is Shown. A Partial Sectional View is Shown in Fig.
2. The Relation of the Engine and Bed, Shaft and Fittings, Shaft Block,
Shaft Log, and Rudder are Shown. The Construction Diagram, Fig. 3, is
Described in Detail in the Text. A Larger-Scale View and a Section of the
Shaft Block are Indicated in Fig. 4, and Fig. 5 Illustrates the Engine Bed
with Dimensions and Fastening Holes
A detail of the shaft bearing R is shown in Fig. 4. The hole to

receive the shaft must be bored accurately, and the use of the
template, as with the boring of the shaft log, is advisable. Flanged
metal bearings are provided to take up the wear in the bearing block.
The method of fastening the block, as shown in the detail view,
insures a rigid bearing with a minimum of holes through the bottom
of the canoe. A U-bolt, T, binds the double angle brace U and the
block firmly to the keel. The angles of the brace are fixed into the
sides of the canoe with bolts, and a bolt at the stern end of the block
supports it further. The block should be placed so that it will bear on
three ribs and must be fitted to the curve of the canoe.
The rudder is made of sheet metal supported on a rod or pipe. Its
general dimensions are shown in Fig. 2. The fan of the rudder is
riveted to its supports and rests in a bearing strip of ¹⁄₄ by 1-in. strap
iron, which is shaped as a guard for the propeller. The upper bearing
of the rudder post is formed from a strip of iron, bolted to the stern,
and the upper guide bar, to which the ropes are attached, is cut from
an iron strip.
The propeller is 8 in. in diameter, but may be installed of a size
suitable to the power, speed, and type of the motor used. The
stuffing box V, Fig. 2, the bearings for the bearing block R, the intake
strainer W, the exhaust outlet X, Fig. 1, and the shaft coupling Y are
all of manufactured types that may be purchased of marine-supply
houses.
The intake strainer W is placed in the bottom directly below the
pump Z. The exhaust outlet X is placed above the water line, and a
muffler should be installed to avoid noise from the exhaust
explosions. The exhaust may be conducted under water or to a point
near the stern. No indication is given for the placing of the gasoline
tank, the supply pipes, electrical-energy source, and wiring. The tank
may be placed in the stern of the canoe high enough to provide a
good flow. A magneto may be used to give current for the sparking
circuit, or batteries may be provided. They may be placed at any
point convenient, and should be incased in a waterproof container.
In assembling the parts care must be taken not to wrench the shaft
or other pieces out of line, and in general, it is well to fix
nonadjustable parts solidly when they are fitted into place. This
applies particularly to the engine bed and the shaft log. The bearing
block may be adjusted vertically by adding packing, or by reducing
the lower surface. The rudder and its fittings may be made in regular
course, but should not be fitted until the power unit and driving
mechanism is in place finally. The propeller may be protected from
possible injury by laying it aside until needed. All the openings in the
hull through which bolts or other fastenings are placed should be
packed with red lead or other waterproof packing. The working parts
and finished metal surfaces should be oiled or greased thoroughly as
the parts are assembled, and the unfinished metal parts painted with
red lead. This will protect them from moisture and aid in the smooth
operation of the mechanism.
How to Make a Fluorescent Screen
Many experimenters have occasion to use a fluorescent screen,
particularly those interested in X-ray work. Such a device is quite
expensive if purchased, and may be made as follows:
Mix 1 oz. each of common salt, sodium tungstate, and calcium
chloride. Place the mixture in a crucible and heat it dull red in a coal
fire, for several hours. It will melt into a clear liquid, and should then
be removed and permitted to cool. The liquid will crystallize into a
hard glasslike mass. Break this out of the crucible and crush it into
small pieces. Put them into a jar of clear water. The sodium chloride
resulting from the chemical change by heating, will gradually
dissolve and the calcium tungstate will fall to the bottom in fine
crystals. Wash this precipitate until all trace of the salt disappears;
then pour the crystals upon a sheet of filter or blotting paper to dry.
After drying, place them in a mortar and grind them to a fine powder,
when they will be ready for use.
To make the screen proper, procure a piece of thin white
cardboard of the size desired. The calendered board known as
three-ply is satisfactory. Paint the cardboard on one side with a thick
solution of gum arabic in water, or better still, with celluloid dissolved
in amyl acetate. Permit the gum to become “tacky” before dusting
with the chemical. The latter process requires care, to produce an
even layer on the cardboard, and it is advisable to practice with
ordinary salt before attempting it on the cardboard for the screen.
The calcium tungstate should be placed in a dry jar, and a piece of
fine muslin fixed over the mouth of it. The chemical may be dusted
over the surface with this sieve jar.
Shake off the superfluous crystals and permit the screen to dry
thoroughly. Fasten a piece of mica, or sheet celluloid, over the
sensitized surface to prevent damage to it. Mount the sensitized
cardboard in a wooden frame of suitable size and arrange a hood
around its edges to cut out unnecessary light. The sensitive side of
the screen is, of course, held toward the observer when the
apparatus is used.—Contributed by Chester Keene, Hoboken, N. J.
Preventing Wire Mesh from Rising between
Fence Posts
Fences which inclose pastures for hogs, or other smaller animals,
are usually stretched to give rigidity and strength. Often the
adjustment of the wire, after being put into place, causes it to rise
from the ground between the fence posts, permitting the animals to
escape. An effective method of holding the wire close to the ground
is shown in the sketch. A peg, notched near its upper end, is driven
into the ground so that the lower edge of the wire mesh is held fast in
the notch.—Contributed by O. B. Laurent, New Roads, La.
The Notched Stake Holds the
Wire Mesh Down between the
Posts Where It Has a Tendency
to Rise from the Ground
Jig-Saw Table for Vise
Those who have occasional work to be done with a jig saw will find
the simple device shown in the sketch convenient. It provides a table
for sawing light work. By holding it in a vise, as shown, a rigid
support may be had. The table is made of a rectangular piece of ³⁄₄-
in. wood, 8 in. wide and 10 in. long. At one end, a strip, 1 in. square,
is attached for clamping in the vise. The other end is notched to
provide a place for the saw while in use.—Contributed by Victor A.
Rettich, New York, N. Y.
The Jig-Saw Table Provides a Rigid Support for Light Fretwork

An Emergency Dark-Room Light
The traveling man who “lives in a suitcase” and at the same time
wishes to enjoy the pleasures of amateur photography sometimes
experiences difficulty in developing films in a hotel room. Soup plates
borrowed from the steward, or even the bowl pitcher and the ice-
water pitcher in the room, can be used for development, but it is very
hard to improvise a ruby lamp. My emergency lamp is a small vest-
pocket flash lamp over which two yellow envelopes, one inside of the
other, are slipped, as shown. The lower edges are cut perfectly
square and rest on the table, or shelf, in the closet, and all white light
is excluded. At night, the shades may be drawn, and a yellow-paper
sack may be tied around the electric light.—Contributed by J. L.
Pinkston, Granite Hill, Ga.
An Ice Creeper
The illustration shows a one-piece ice creeper for the heel of a

boot or shoe. It is made from sheet steel with the arms bent up to
receive a strap for buckling it in place on the boot heel. The zigzag
cuts in the bottom part are turned down for engaging the ice.—
Contributed by Chas. S. Snell, Lewiston, Me.
¶In machine work a way must be provided for removing dowel pins
before they are driven in place.
Waterproofing for Fish Lines
Dissolve ¹⁄₂ oz. of orange shellac in ¹⁄₂ pt. of alcohol, and add 1
teaspoonful of Venice turpentine, the same quantity of raw linseed
oil, and 2 oz. tincture of benzoin. Shake well, and set in a varnish
can in hot water.
Soak the coiled line in the varnish for two hours, then hang it up to
dry. Thin the varnish with alcohol, and repeat the dipping. When the
line is dry, rub it down well with a wool rag greased with tallow. Silk
lines treated in this manner are pliable, and the fibers of the silk are
so united by the varnish that the strength of the line is almost
doubled.
Making Chest Lock More Secure
As a rule, ordinary chest locks cannot be relied upon, since almost

any kind of a similar key will unlock them. I found a good remedy by
taking out the pin on which the key fits, and making a new one twice
as long as the one removed, then drilling a hole in the key deep
enough to fit over the new pin. In case the pin extends too far, a
piece of wood block, with a hole in it to admit the key, can be
fastened over it to prevent bending the pin. No ordinary key will pass
on the pin far enough to turn the lock.—Contributed by Chas. G.
England, Washington, Pa.
Driving Screws in Hard Wood
Keep the supply of screws in a box containing a small amount of
powdered soapstone. Shake the box occasionally, and the screws
will be dusted with the powder, which acts as a lubricant. This is a
much cleaner and more convenient method than the ordinary one of
rubbing each screw on a bar of soap before driving it in hard wood.
Paddling Your Own Canoe
by
Stillman Taylor
PART I—
Kinds of Canoes
Theprose,
charm of the birchen canoe has long been sung in verse and
and while the bark that the Indian used has been
supplanted by a more perfect type of modern manufacture, the
popularity of this, the most graceful of water craft, has increased with
years, until today we find the canoe the choice of thousands of
recreation seekers who paddle about in park lakes and quiet
streams, or spend their vacations in cruising down rivers and other
attractive waterways—sometimes within the environs of towns and
villages, and again dipping paddles in the wilderness streams of the
far north. True, the modern canoe is a distinct product of the
twentieth century, and while it is so largely used at summer resorts, it
nevertheless retains all the good points of the old, while embodying
numerous improvements which fit it even better for wilderness travel
than the Indian model after which it was patterned. The noteworthy
increase in the number of canoeists in the past dozen years is good
evidence that this natty craft is fast coming into its own, and as more
and more outdoor men and women understand its possibilities and
limitations and become proficient in handling it, the long-rooted fear
and distrust with which the uninformed public regard the canoe, will
pass away. As a matter of fact, accidents ever follow in the wake of
ignorance and carelessness, and while there are very few expert
gunners injured by firearms, and still fewer experienced canoeists
drowned, there are numerous sad accidents constantly occurring to
the reckless and foolhardy, who do not know how to handle a
weapon, nor understand the first thing about paddling a canoe. Let
us consider then, the practical side of the subject, the choice of a
suitable canoe and the knack of handling it in a safe and efficient
manner.
If one would experience in full measure the many-sided charm of
paddling, he should get a good canoe. Unlike other and heavier
water craft, the canoe is a lightly balanced and responsive
conveyance, which may be cranky and dangerous, or safe and
stable, according to the model, the skill of the builder, and the
dexterity of the paddler. There are canoes and canoes, of varying
models and sizes, and constructed of many materials, and while all
may serve as a means of getting about in the water, the paddling
qualities include numerous little idiosyncrasies which serve to
differentiate canoes as well as men. In fact, this light and graceful
craft may be properly viewed as the highest type of boat building,
since it must be fashioned strong but light; it must be steady when
going light; capable of carrying comparatively heavy loads; draw little
water, and it must be honestly constructed of good material to stand
up under the hard usage which every canoe is subjected to, whether
used for summer paddling, or upon long hunting and shooting trips.
Three types of canoes are in common use by experienced
canoeists, the birch-bark, the all-wood, and the canvas-covered
cedar canoe. The birch-bark, by reason of its rougher workmanship,
is slow under the paddle, is easily injured, and it grows heavier and
more difficult to handle every time it is used. The all-wood canoe is
most expensive to buy, and though swift under the paddle, is too
easily injured and too difficult to repair for rough and ready use. The
cedar-planked canoe which is covered with filled and painted canvas
is for many reasons the best all-around craft-attractive enough for
park use, and stout enough for use in rapid water and for cruising in
northern lakes and rivers.
How to Select a Birch-Bark Canoe
The Indian-made birch-bark canoe costs about $1 a foot and is

fashioned of birch bark over an ash, or spruce, frame. The bark is
not nailed to the frame, but is sewed together with boiled spruce, or
tamarack, roots, split to a suitable size. To give the proper shape to
the canoe a double row of stakes are firmly planted in the ground
and the spruce frame is sprung between them. The bark is put on
inside out, and the work of sewing together is done while the bark is
fresh, or immediately after it is stripped from the tree. The seams are
afterward made water-tight by smearing well with spruce gum, which
hardens quickly and makes a fairly good joint. The Indian model is a
good one so far as the freeboard, width of beam, and flaring stems
are concerned, but the curved bottom makes it extremely cranky and
dangerous for the novice to handle. Be sure to see that the birch-
bark canoe is fashioned with a flat, straight bottom, which makes the
craft steadier and less inclined to veer about under the stroke of the
paddle. In an expert’s hands the round bottom will be found a
decided advantage, making it faster to paddle and more easily
turned and steered in swift and rough water. Many prefer the three-
piece bottom, but the bottom made of a single piece of bark is
stronger and less likely to open up and leak. All birch canoes will
warp and twist somewhat, and it is practically impossible to find one
that is straight and true. The birch-bark canoe has many limitations
and not a few weaknesses, but if one has the good luck to find a
good one, and treats it fairly, it will prove a safe and dry craft for
many hundreds of miles’ travel. Of course, one must carry a kettle of
pitch for making repairs, and be content to travel somewhat slower
than with modern canoes, but this may not be a disadvantage. Birch
canoes have no seats, as the Indian kneels when paddling, but a low
thwart, or seat, is easy to put in at the bow and stern, if one prefers
the white man’s paddling position.
All-Wood or Peterborough Canoe
This type of craft is much used in Canada along the St. Lawrence
River, and to a much less extent by American sportsmen, owing to
its higher cost, and its tendency to break and cause a leak. Of
course, the all-wood canoe is a good craft, but everything
considered, there can be no question in the minds of canoeists who
are acquainted with all types of canoes, that the all-cedar or
basswood craft is less dependable than the canvas-covered cedar
canoe. The Peterborough type—so called from a Canadian city of
this name where many wood canoes are made—with its relatively
low ends and straight sides with but little sheer and tumble home, is
the model commonly used by practically all manufacturers of the all-
wood canoe. While a boat of this kind can be, and often is, used in
rough-water lake paddling as well as in wilderness travel, the all-
wood canoe is better suited for club use, and in the wider and more
quiet-flowing streams and lakes.
The Best All-Around Craft, for Two Men and a Reasonable Amount of Camp
Duffle, Is a Canvas-Covered Cedar Canoe, 16 Feet Long, 32-Inch Beam, and
12 Inches Amidships, Weighing About 60 Pounds
The Canvas-Covered Cedar Canoe
The canvas-covered cedar canoe, when rightly made of the best

material, is by all odds the best paddling craft afloat, being strong
and light, with a hull so smooth that it is swift to paddle, while the
mode of construction makes a very stiff craft, which will not warp or
twist out of shape. Moreover, it will stand a vast amount of hard
usage and abuse, while repairs are quickly and neatly done by the
stream side. In the making of a first-class canoe of this type, the ribs
are first steamed and then bent and fitted over a solid form; cedar
being used for the ribs and planking; spruce for the gunwales, and
white ash, or oak, for the stems and thwarts. In a canoe built
according to my instructions, each plank runs to the full length of the
craft and all are beveled and lapped together, thus making a
perfectly smooth and almost water-tight canoe, before the canvas is
cemented on its surface. The canvas is thoroughly waterproofed
before it is put on, then it is drawn tightly over the planking, and
several coats of filler and the final finish of paint are applied, after
which it is rubbed down.
The well-made canvas-covered canoe is, if properly designed, a
pretty good facsimile of the representative Indian model in that it
possesses all the good points of the birch-bark canoe, but is more
substantially constructed, of better and more durable material, and
more finely finished. In making the selection, it is necessary to pay a
fair price to obtain a good craft, and while various manufacturers
supply canoes of similar types at different prices, some of them are
so inferior that they will scarcely stand a season’s use. Of course,
the use to which a canoe is put will influence the selection. If the
craft is wanted for long service on hunting and fishing trips, a high-
grade canoe of plain finish is the logical choice. If the canoe is for
club use, a highly finished craft with mahogany trimmings may be
preferred. A canoe for occasional use on some quiet lake or small
stream may be selected from the cheaper kinds, which will, no
doubt, answer every purpose. However, most manufacturers list
what they call an “A” and a “B” grade. The “A” grade provides
selected-cedar ribs and planking; oak for gunwales, stems, thwarts
and seats selected from the finest material, and the finish the best
that can be procured, while the “B” grade is identical in model,
canvas and paint, but the material not quite so clear or free from
minor defects, though for all practical purposes it will render as much
service and give fully as much satisfaction as the first, or “A,” grade.
A little saving may be made by selecting the second-grade canoe,
having most of the money invested in the canoe and not so much in
the finer finishings. The ordinary construction provides for the
ordinary solid topwale, but the open gunwale is sometimes preferred,
because the openings make washing easy, all sand and dirt running
out freely between the wales. This construction detail is supplied by
most manufacturers, when specified, at a slight additional cost.

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CO2 Hydrogenation Catalysis Yuichiro

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2 Homogeneously Catalyzed CO2 Hydrogenation to Formic Acid/Formate

2.3.2 Ru Complexes with N,N- and N,O-ligands 40

3 Homogeneously Catalyzed CO2 Hydrogenation to Formic Acid/Formate with

4 Catalytic Homogeneous Hydrogenation of CO2 to Methanol 89

5 Theoretical Studies of Homogeneously Catalytic Hydrogenation of Carbon

5.3 ­ ydrogenation of CO2 to Formic Acid/Formate

6 Heterogenized Catalyst for the Hydrogenation of

7 Design and Architecture of Nanostructured Heterogeneous Catalysts

8 Heterogeneously Catalyzed CO2 Hydrogenation to Alcohols 207

8.2.6 Beyond Industrial Cu/ZnO/Al2O3 Catalysts 223

9 Homogeneous Electrocatalytic CO2 Hydrogenation 237

10 Recent Advances in Homogeneous Catalysts for Hydrogen Production

10.2.2 Aqueous Solution Systems 270

July 2020 Yuichiro Himeda

1.1 ­Direct Use of CO2

CO2 Hydrogenation Catalysis, First Edition. Edited by Yuichiro Himeda.

Reference Technology Scenario

1.2 ­Chemicals from CO2 as a Feedstock

Table 1.1 Chemicals produced commercially from CO2 .

Chemical Scale of production/ton

Anthropogenic CO2 emissions (2018) 33 100 000 000

Source: From Omae [6]. © 2012 Elsevier.

1.3 ­Application and Market Studies of CO2

Hydrogenation of CO2 could be an efficient option for developing more environment-

1.3.1 Formic Acid/Formate

Table 1.2 Characteristics of various energy vectors.

Energy Approx. price

Methanol 15.8 15 64.55/–97.68 470/15 (open) 16.9

1.3.4 Energy Storage

1.4 ­Supply of Materials

1.4.1 CO2 Supply

Table 1.3 Concentration of CO2 and contaminants from various sources.

Source Amount/Mton CO2 concentration/% Impurities

Ethanol fermentation [28, 30] 50 99 EtOH, MeOH, H2O, H2S

Table 1.4 CO2 capture technologies.

Capture technology Technical principle

Source: Based on Styring [33].

1.4.2 Energy and H2 Supply

1.5 ­Political Aspect: Tax

1.6 ­Conclusion and Perspectives

(i) Supply of H2 and power from renewables.

150 Coal (industrial)

In addition, critical evaluation from an LCA perspective will be necessary.

32 CO2 Emissions from Fuel Combustion (2019). https://www.iea.org/subscribe-to-data-

Homogeneously Catalyzed CO2 Hydrogenation to Formic

CO2 Hydrogenation Catalysis, First Edition. Edited by Yuichiro Himeda.

Scheme 2.1 Tautomerizable ligands for functional complexes.

of tautomerizable ligands endow complexes with versatility for catalytic hydrogenation. In

2.2.1 Ir Complexes with N,N-ligands

Figure 2.1 Proton-responsive ligands used for CO2 hydrogenation.

–2.5 –2 –1.5 –1 –0.5 0 0.5

Table 2.2 pKa values of functional OH groups in complexes.

Complex pKa of OH References

[Cp*Ir(4DHBP)(OH2)]SO4 5.2 [49]

Pendant-Base Effects As shown in Figure 2.2, the activity of [Cp*Ir(6DHBP)(OH2)]2+

5.3 ydrogenation of CO2 to Formic Acid/Formate

1.1 Direct Use of CO2

1.2 Chemicals from CO2 as a Feedstock

1.3 Application and Market Studies of CO2

1.4 Supply of Materials

1.5 Political Aspect: Tax

1.6 Conclusion and Perspectives