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1 Chapter 1Figure 1.1 Atmospheric CO₂ concentration at Mauna Loa Observatory.Figure 1.2 IEA 2 °C Scenario (2DS) in Energy Technology Perspectives 2017....Figure 1.3 Global methanol demand in 2018.Figure 1.4 CO₂ emissions from fuel combustion.Figure 1.5 Low‐carbon electricity generation by source in 2017.Figure 1.6 Levelized cost of energy comparison: Renewable energy versus conv...Figure 1.7 Carbon tax rate per ton of emitted CO₂.

2 Chapter 2Scheme 2.1 Tautomerizable ligands for functional complexes.Figure 2.1 Proton‐responsive ligands used for CO₂ hydrogenation.Figure 2.2 Correlation between initial TOFs and σ_p ⁺ values of substituents (...Scheme 2.2 Acid–base equilibrium between hydroxy and oxyanion forms and reso...Scheme 2.3 Proposed mechanism for H₂ heterolysis assisted by the pendant bas...Figure 2.3 Proton‐responsive N,N‐ligands with pendant OH groups.Figure 2.4 Selected N,N‐ligands with NH groups for CO₂ hydrogenation.Scheme 2.4 Deprotonation and resonance of N,N‐ligands with NH groups in comp...Figure 2.5 Selected N,N‐ligands with OH and NH groups for CO₂ hydrogenation....Scheme 2.5 In situ–prepared and isolated picolinamide complexes for CO₂ hydr...Scheme 2.6 Resonance structures of picolinamide complex.Figure 2.6 NHC Ir complexes developed by Peris et al.Figure 2.7 Pincer Ir complexes developed by Nozaki et al.Scheme 2.7 Proposed mechanism for the hydrogenation of CO₂ by 7.Figure 2.8 Pincer Ir complexes with NH group.Scheme 2.8 Proposed mechanism for CO₂ hydrogenation with 15b.Figure 2.9 Phosphorous ligands and Ru complexes for CO₂ hydrogenation.Scheme 2.9 Biphasic system for CO₂ hydrogenation developed by Leitner et al....Figure 2.10 Ru complexes with N,N‐ and N,O‐ligands for CO₂ hydrogenation.Scheme 2.10 Pincer Ru complexes for H₂ and CO₂ activation.Scheme 2.11 Experimentally observed transformations of Ru–PNP complexes in t...Scheme 2.12 CO₂ hydrogenation with Ru‐CNC pincer complex 41.Figure 2.11 Pincer complexes for CO₂ hydrogenation employed by Prakash et al...Scheme 2.13 CO₂ capture and conversion to ammonium formate.Scheme 2.14 Integrated CO₂ capture and utilization system developed by Praka...Figure 2.12 Ru‐CNC complexes for CO₂ hydrogenation.Figure 2.13 Pincer Ru complexes for CO₂ hydrogenation.Figure 2.14 Rh complexes and phosphine ligands for CO₂ hydrogenation.Scheme 2.15 Biphasic system for CO₂ hydrogenation developed by Leitner et al...Figure 2.15 Biometric Rh complexes for CO₂ hydrogenation.Figure 2.16 Rh complexes with C,C‐ and N,N‐ligands.

3 Chapter 3Figure 3.1 Abundance (ppm) of mid‐ and late transition metals in Earth's cru...Scheme 3.1 Proposed catalytic cycle for CO₂ hydrogenation in the presence of...Scheme 3.2 Proposed mechanism for the role of additives in TON enhancement u...Scheme 3.3 Proposed catalytic cycle for CO₂ hydrogenation in the presence of...Figure 3.2 Fong and Peters' iron complexes 3–8 bearing tri‐ and tetrad...Scheme 3.4 Proposed catalytic cycle for CO₂ hydrogenation in the presence of...Figure 3.3 Fe(II) complexes 9 and 10 bearing the tetradentate phosphine 1,1,...Figure 3.4 NaHCO₃ hydrogenation to formate by [FeH(rac‐P4)]⁺ (12), path B....Figure 3.5 Fe catalysts derived from Knölker's complex motif.Scheme 3.5 Proposed catalytic cycle for CO₂ hydrogenation in the presence of...Scheme 3.6 Proposed catalytic cycle for CO₂ hydrogenation showing possible M...Scheme 3.7 Proposed catalytic cycle for CO₂ hydrogenation starting from 25....Scheme 3.8 Proposed mechanism for Li co‐catalyst promoting effect starting f...Scheme 3.9 Proposed catalytic mechanism for Li‐assisted CO₂ hydrogenation wi...Figure 3.6 Catalyst recycling scheme (a) and observed TOFs (b) using Ru‐MACH...Scheme 3.10 Proposed catalytic mechanism for CO₂ hydrogenation with 39.Scheme 3.11 Proposed catalytic cycle for CO₂ hydrogenation starting from 41....Scheme 3.12 Proposed catalytic cycle for CO₂ hydrogenation starting from 45,...Figure 3.7 Multidentate ligands screened for CO₂ hydrogenation in combinatio...Scheme 3.13 Proposed catalytic cycle for CO₂ hydrogenation starting from bim...Scheme 3.14 Simplified catalytic cycle for CO₂ hydrogenation starting from t...Scheme 3.15 Proposed (simplified) competing catalytic cycles for CO₂ hydroge...Figure 3.8 Substituted‐bipyridine Mn(I) bromotricarbonyl complexes 67–70...Scheme 3.16 Proposed catalytic cycles for CO₂ hydrogenation in the presence ...Scheme 3.17 Proposed reaction pathway for CO₂ functionalization with ethene ...Scheme 3.18 Proposed catalytic cycles for CO₂ hydrogenation in the presence ...Scheme 3.19 Synthesis of κ²‐formato complex91.

4 Chapter 4Figure 4.1 Carbon‐neutral cycle in the context of methanol economy.Figure 4.2 CO₂ hydrogenation to methanol and related reactions.Figure 4.3 Different routes for obtaining methanol from CO₂.Figure 4.4 First reported homogeneous CO₂ to methanol system catalyzed by RuFigure 4.5 Step‐wise hydrogenation of CO₂ to methanol through carbonate, car...Figure 4.6 Indirect CO₂ hydrogenation to methanol through urea derivatives....Figure 4.7 Molecular mechanism of hydrogenation by complex C‐1.Figure 4.8 Indirect CO₂ to methanol route through cyclic carbonates.Figure 4.9 Hydrogenation mechanism with complex C‐3.Figure 4.10 Cascade catalysis of CO₂ to methanol.Figure 4.11 Ruthenium‐catalyzed CO₂ to methanol system developed by Leitner ...Figure 4.12 Mechanistic cycle of CO₂ to methanol with C‐8 in the absen...Figure 4.13 Cobalt‐catalyzed CO₂ to methanol system.Figure 4.14 Combined CO₂ capture and conversion to methanol through oxazolid...Figure 4.15 Amine‐assisted CO₂ to methanol process.Figure 4.16 Morpholine‐mediated CO₂ to methanol through formamide.Figure 4.17 Carbon capture and utilization cycle to form methanol from CO₂....Figure 4.18 PEHA‐assisted CO₂ to methanol.Figure 4.19 Conversion of CO₂ from air to methanol.Figure 4.20 Biphasic system for catalyst and amine recycling.Figure 4.21 Catalyst and amine recycling based on amine immobilization.Figure 4.22 Change in methanol TON with different substitutions on the P ato...Figure 4.23 Proposed mechanism of amine‐assisted CO₂ to methanol process.Figure 4.24 Amine‐assisted CO₂ to methanol system reported by Everett and Wa...Figure 4.25 PEI‐mediated CO₂ to methanol through formamides.Figure 4.26 Manganese‐catalyzed CO₂ hydrogenation to methanol.Figure 4.27 CO₂ to methanol via formic acid disproportionation.

5 Chapter 5Figure 5.1 (a) The structural diagrams of the active sites of three types of...Scheme 5.1 Yang and Hall's mechanism for H₂ activation catalyzed by [Fe]‐hyd...Figure 5.2 Two typical ways for CO₂ insertion into a metal–hydride bond.Scheme 5.2 Two plausible cycles for the dehydrogenation of formic acid catal...Scheme 5.3 Sakaki's mechanism for the hydrogenation of CO₂ to formic acid ca...Scheme 5.4 Nozaki and coworkers' plausible mechanism for hydrogenation of COScheme 5.5 Mechanism for the hydrogenation of CO₂ catalyzed by (PNP)IrH₃ pro...Scheme 5.6 Yang's mechanism for the hydrogenation of CO₂ to HCOO⁻ cata...Scheme 5.7 Hazari and coworkers' mechanism for the hydrogenation of CO₂ cata...Scheme 5.8 Thiel and coworkers' mechanism for the hydrogenation of CO₂ catal...Scheme 5.9 Himeda and coworkers' proton‐switchable iridium catalyst for reve...Scheme 5.10 Himeda and coworkers' mechanism for the hydrogenation of CO₂ cat...Scheme 5.11 Mechanism for H₂ heterolysis assisted by the pendant base and wa...Scheme 5.12 The transformations of H₂ and CO₂ catalyzed by (PNP)Ru complexes...Scheme 5.13 Pidko and coworkers' mechanism for CO₂ hydrogenation to formates...Scheme 5.14 The overall process of CO₂ hydrogenation catalyzed by Ru complex...Scheme 5.15 Proposed overall mechanism for the reduction of bicarbonate to f...Scheme 5.16 Ke and coworkers' mechanism for the hydrogenation of CO₂ catalyz...Scheme 5.17 Predicted catalytic cycles with the monohydride (Path I) and dih...Scheme 5.18 Predicted mechanism for CO₂ hydrogenation catalyzed by PNP–Fe co...Figure 5.3 The active site structure of [Fe]‐hydrogenase reported by Shima a...Scheme 5.19 Predicted mechanism for the hydrogenation of CO₂ to formamide ca...Figure 5.4 Optimized transition state structures of two‐proton transfer for ...Figure 5.5 Liu, Dubois, and Bullock’s Mn (a) and Co (b, c, and d) complexes ...Figure 5.6 Yang and co‐workers' computationally designed Fe (a, b), Mn (c), ...Scheme 5.20 Yang and coworkers' mechanism of the hydrogenation of CO₂ to met...Scheme 5.21 Yang and coworkers' mechanism for the hydrogenation of CO₂ to fo...Scheme 5.22 Yang and coworkers' mechanism for the hydrogenation of formic ac...Scheme 5.23 Yang and coworkers' mechanism for the hydrogenation of formaldeh...Figure 5.7 Newly constructed iron, cobalt, and manganese complexes [81].Figure 5.8 Meyer's monomeric amidate‐ligated Fe complex (a) [82], Hitomi's m...Scheme 5.24 Yang and coworker's mechanism for the formation of methanol from...Scheme 5.25 Rueping and coworkers' mechanism for the hydrogenation of ethyle...

6 Chapter 6Figure 6.1 Schematic representation for synthesis of silica (a) and PS (b) s...Figure 6.2 Schematic representation for synthesis of “Si”‐(CH₂)₃NH(CSCH₃)‐Ru...Figure 6.3 Schematic representation for synthesis of Ir‐PN/SBA‐15.Scheme 6.1 Synthesis of PEI‐PN/Ir.Figure 6.4 Schematic representation for synthesis of Ir‐PN‐PEI@TNT(Na⁺).Figure 6.5 Schematic representation of Ru/LDH.Figure 6.6 Schematic representation for synthesis of lutidine‐derived bis‐NH...Figure 6.7 Schematic representation for synthesis of mbpyOH‐[Ir^III]‐UIO and ...Figure 6.8 Schematic representation of RuCl₃@MIL‐101(Cr)‐R (a) and Ru3‐NHC‐M...Figure 6.9 Schematic representation for synthesis of TB‐MOP‐Ru.Figure 6.10 Schematic representation for synthesis of ML _x (bpy‐CTF)X]X (a) an...Figure 6.11 Schematic representation for synthesis of [IrCp*(HBF‐2)Cl]Cl....Figure 6.12 Scheme of CTF sphere preparation (a) and SEM image of CTF sphere...Scheme 6.2 Representative structure of porous phosphine polymers (a) and the...Figure 6.13 Schematic representation for synthesis of Ir/AP‐POP.Figure 6.14 Schematic representation for synthesis of Phen‐POP‐Ir.

7 Chapter 7Figure 7.1 Selective hydrogenation of CO₂ by RuFe nanoparticles in different...Figure 7.2 Microenvironmental engineering of Pd nanoparticle catalysts using...Figure 7.3 A possible reaction pathway for CO₂ hydrogenation over a PdNi bim...Figure 7.4 (a) Molecular structure of graphitic carbon nitride (circled part...Figure 7.5 Possible reaction mechanism for bicarbonate hydrogenation over Pd...Figure 7.6 (a) Synthetic approaches to tailor the basic properties of g‐C₃N₄ Figure 7.7 (A) FT‐IR spectra of Au/Al₂O₃ catalyst treated with (a) DMF/NEt₃ ...Figure 7.8 (a) Comparison of the catalytic activities of a series of support...Figure 7.9 (a) Possible reaction mechanism for CO₂ hydrogenation to formic a...Figure 7.10 (a) Schematic illustration for the preparation of PdAg/SBA‐15‐Am...Figure 7.11 Proposed synergistic mechanism for the hydrogenation of CO₂ to f...Figure 7.12 Ru K‐edge FT‐EXAFS spectra and schematic illustration of Ru/LDH....Figure 7.13 (a) Relationship between TON‐based on Ru during CO₂ hydrogenatio...Figure 7.14 Energy profile for CO₂ hydrogenation to formic acid on Cu‐dG. Di...

8 Chapter 8Figure 8.1 Schematic diagrams of the CAMERE process; (a) the original proces...Figure 8.2 The “George Olah Carbon Dioxide to Renewable Methanol Plant” of C...Figure 8.3 Liquid formation in a view cell during methanol synthesis of H₂, ...Figure 8.4 Equilibrium CO₂ conversion and methanol selectivity at different ...Figure 8.5 Types of catalyst material reported for CO₂ hydrogenation to meth...Figure 8.6 Synthesis methods of Cu/ZnO‐based catalysts. The percentage was c...Figure 8.7 Schematic overview of the multistep synthesis route for Cu/ZnO ca...Figure 8.8 Simplified preparation scheme of Cu/ZnO catalyst from zincian mal...Figure 8.9 Microstructural features revealed with transmission electron micr...Figure 8.10 General scheme for methanol synthesis over Cu/ZnO‐based catalyst...Figure 8.11 Proposed reaction mechanisms for the CO₂ hydrogenation toward me...Figure 8.12 Proposed reaction mechanisms for the CO₂ hydrogenation toward et...

9 Chapter 9Figure 9.1 Line drawings of (a) [M(bpy)₂X₂]⁺, (b) M(Cp*)(bpy)Cl]⁺, (c) [Rh(d...Figure 9.2 Line drawings of (a) [Ir(POCOP)H₂(MeCN)]⁺, (b) [Ir(POCOP)′H₂(MeCN...Figure 9.3 Line drawings of [IrCp*(L)(X)] ⁿ⁺, where L is varied.Figure 9.4 Line drawings of (a) [Ru(bpy)₂(CO)₂]²⁺, (b) [Os(bpy)(CO)H]⁺, (c) ...Figure 9.5 Line drawings of (a) [Fe(dophen)L₂]⁺, (b) [Fe( ^tBudhbpy)Cl], (c) [...Figure 9.6 Line drawings of (a) [Ni(cyclam)]²⁺, (b) [Ni₂(biscyclam)]⁴⁺, and ...Figure 9.7 Line drawings of [Ni(2H‐qpdt ^x )₂)] x = a, b, c.Figure 9.8 Line drawings of (a) [Fe₆Mo₂S₈(SEt)₈]³⁻, (b) [Fe₄S₄(SR)₄]²⁻...Figure 9.9 Terminal hydride insertion pathways.Figure 9.10 Bridging hydride insertion pathways.Figure 9.11 Electrocatalytic reduction of CO₂ to formate by [Co(P^R ₂N^R′ Figure 9.12 Electrocatalytic reduction of CO₂ to formate with [Ir(PN^HP)H₃]....Figure 9.13 Electrocatalytic reduction of CO₂ to formate with [Fe₄N(CO)₁₂]⁻...Figure 9.14 Definition of hydricity.Figure 9.15 Driving force for hydride transfer between L _n ‐M and CO₂.Figure 9.16 Line drawings and hydricity of (a) H‐[Fe₄N(CO)₁₂]⁻, (b) H‐...Figure 9.17 Electrochemical reduction of CO₂ to methanol using [Fe(PP₃)(MeCN...

10 Chapter 10Figure 10.1 Schematic representation of the setup used for continuous hydrog...Chart 10.1 Ru catalysts for FA dehydrogenation.Chart 10.2 Ligand structures of rac‐P4 and meso‐P4.Chart 10.3 Pincer ruthenium complex for FA dehydrogenation.Figure 10.2 Reaction mechanism for Ru‐4.Chart 10.4 Selective Ir catalysts for FA dehydrogenation.Figure 10.3 Reaction mechanism of FA dehydrogenation (FADH) via Ir‐2....Figure 10.4 Plausible reaction mechanism of bisMETAMORPhos catalyst, Ir‐3...Figure 10.5 Proposed mechanism for FA dehydrogenation using Fe/PP₃ catalysis...Chart 10.5 Selective well‐defined iron catalysts.Figure 10.6 Proposed reaction mechanism for FA dehydrogenation using an iron...Chart 10.6 Water‐soluble phosphine ligands for aqueous FA dehydrogenation wi...Figure 10.7 Hammett plots of FA dehydrogenation with Cp*Ir catalysts bearing...Chart 10.7 Selective Ir catalysts for FA dehydrogenation.Figure 10.8 Time courses of the volume and rate of released gases via FA deh...Figure 10.9 Time courses of volume of released gases (left axis) and rate of...Chart 10.8 Catalyst structures for MeOH dehydrogenation.Figure 10.10 Plausible reaction mechanism for methanol dehydrogenation.Figure 10.11 Proposed reaction mechanism for MeOH dehydrogenation using Ru‐6...Figure 10.12 Proposed reaction mechanism for MeOH dehydrogenation usingIr‐15...Figure 10.13 Proposed reaction mechanism for MeOH dehydrogenation using Fe ‐4...