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7 Chapter 13Table 13.1 Reaction categories involved in photo‐mediated catalysis and related Gibbs free energy.Table 13.2 Hydrogen or methanol yield in methane steam reforming reaction using various photocatalysts.Table 13.3 Methane coupling reaction with photo‐assisted catalysis.

8 Chapter 14Table 14.1 Photocatalytic conversion of processed lignin in literatures. Source: Liu et al. [49]. © 2019, The Royal Society of Chemistry.Table 14.2 Photocatalytic conversion of cellulose in literatures. Source: Liu et al. [49]. © 2019, The Royal Society of Chemistry.

List of Illustrations

1 Chapter 2Figure 2.1 Schematic of solar fuel feedstocks (CO₂, H₂O, and solar energy) and production path on‐site and/or transported to the solar refinery [4].Figure 2.2 Schematic diagrams of (a) natural photosynthesis and (b) artificial photosynthesis based on molecular systems. Source: Liu et al. [9].Figure 2.3 (a) Traditional catalytic processeson the surface of catalysts. (b) Classic photocatalytic paths over photocatalysts.Figure 2.4 A band‐gap diagram showing the different sizes of band gaps for conductors, semiconductors, and insulators.Figure 2.5 Proposed mechanism of photocatalytic reactions on semiconductor photocatalysts. Source: Ma et al. [16].Figure 2.6 A schematic illustration of the energy correlation between semiconductor catalysts and redox couples in water. CB and VB denote a conduction band and a valence band, respectively. Source: Tu et al. [20].Figure 2.7 (a) Yields of the products produced during the photocatalytic reduction of CO₂ with H₂O and photoluminescence of various Ti/FSM‐16 photocatalysts. (b) Product distribution of CO₂ photoreduction over 1‐TiO₂, 2–10 wt% imp‐TiO₂/Y‐zeolite, 3–1.0 wt% imp‐TiO₂/Y‐zeolite, 4‐ex‐TiO₂/Y‐zeolite, and 5‐Pt‐loaded ex‐TiO₂/Y‐zeolite. (c) Schematic mechanisms of the photocatalytic CO₂ reduction with H₂O on TiO₂. Source: (a) Ikeuea et al. [23]; (b) Anpo et al. [22]; (c) From Anpo et al. [21]. © 1995 Elsevier.Figure 2.8 Schematic cycle for the photosensitized reduction of CO₂ to CH₄. Source: Maidan and Willner [25].Figure 2.9 (a) Calculated band structures and total density of states of BMO‐OVs. Absorptive formats of CO₂ on BMO‐OVs (b) and BMO (c). CO₂ reduction pathways on BMO‐OVs (d) and BMO (e). (f) The diagram of band positions. (g) CH₄ production and the TCEN value for CO₂ photoreduction over the BMO‐OVs and BMO during four hours visible‐light irradiation. (h) Typical time course of CO/CH₄ generated over BMO‐OVs. Source: Yang et al. [30].Figure 2.10 (a) Schematic illustration of the solar‐assisted production of methanol from CO₂ and water through a three‐enzyme cascade. (b) Methanol production as a function of time in multienzymatic systems. (c) Photoelectrochemical production of methanol by TPIEC under various applied potentials under visible‐light illumination. (d) Methanol production of the TPIEC system in various multienzymatic systems with an external voltage of 0.8 V. Source: Kuk et al. [41].Figure 2.11 (a) Mechanism for the reduction of CO₂ by photocatalysis under visible light with a Ru complex and an N‐Ta₂O₅ hybrid catalyst. (b) Turnover number for HCOOH formation from CO₂ over various molecular systems as a function of irradiation time. (c) Schematic mechanism of visible‐light‐driven photocatalytic CO₂ reduction over RuP/NS‐C₃N₄ hybrids. (d) Time courses of photocatalytic CO₂ reduction using RuP/NS‐C₃N₄‐PU0 and RuP/NS‐C₃N₄‐PU90 under visible light (λ > 400 nm). Source: (a) Suzuki et al. [55]; (b) Sato et al. [55]; (c) Tsounis et al. [56]; (d) Tsounis et al. [56].Figure 2.12 (a) Scheme of the photocatalytic CO₂ reduction over CdS/(Cu–Na_xH_2−xTi₃O₇) irradiated by light. (b) Gas evolution rates of C1–C3 hydrocarbons on CdS/(Cu–Na_xH_2−xTi₃O₇) as well as the specific surface area, where the Na/Ti ratios were 0.093 (low), 0.143 (medium), and 0.507 (high). (c–e) Mass spectra of the formed hydrocarbons (methane, ethane, and propane) with the labeling of ¹³C. (f) Proposed elementary reaction mechanisms of photocatalytic CO₂ conversion into hydrocarbons. Source: Park et al. [64].Figure 2.13 Structures of CN before (a) and after (b) doping with carbon chains. (c) Electrochemical impedance spectroscopy (EIS) Nyquist plots under irradiation condition. Inset: Periodic on/off photocurrent response under visible‐light irradiation. (d) Comparison of the photocatalytic CO₂ reduction rate of the samples with different amount of glycine, respectively. Source: Ren et al. [70].Figure 2.14 (a) Gas production under six hours visible‐light irradiation of pure Cu₂O and Cl‐doped Cu₂O samples. (b) Mass spectrum from the ¹⁸O‐labeling H₂O isotope experiments of Cu₂O–Cl‐4. (c) Time‐dependent product evolution over Cu₂O–Cl‐4 under visible‐light irradiation. (d) Stability test of Cu₂O–Cl‐4. (e) Proposed reaction pathways of CO₂RR to CO and CH₄ on Cl‐doped Cu₂O. Source: Yu et al. [83].

2 Chapter 3Figure 3.1 The light‐dependent reactions of photosynthesis produce protons and electrons used in the conversion of CO₂ to carbohydrates (CH₂O) and other organic compounds, while oxidation of these organic compounds (biomass, food, fuels) by respiration or combustion releases the stored solar energy to power the metabolism of non‐photosynthetic organisms and drive human technologies.Figure 3.2 Schematic membrane arrangement of enzymes involved in the light‐dependent reactions of oxygenic photosynthesis. Red arrows indicate the flow of electrons from the primary electron donor H₂O to the final electron acceptor NADP⁺ aided by photoexcitation in photosystems II and I. Electron flow is tied to proton translocation across the membrane. The proton gradient created by accumulation of protons in the interior of the membrane powers the synthesis of ATP.Figure 3.3 Selected types of chlorophyll molecules encountered in natural photosynthesis.Figure 3.4 (a) Side and top view of the light‐harvesting complex LH2 from the purple bacterium R. acidophila 10050 (PDB: 1KZU [24]), showing bacteriochlorophyll a pigments in green and carotenoids (rhodopin glucoside) in orange. (b) Rod structure of c‐phycocyanin from the phycobilisome light‐harvesting antenna of cyanobacterium T. vulcanus (PDB: 3O18 [25]). (c) Light‐harvesting complex II (LHCII) from pea (PDB: 2BHW [26]), showing Chl a pigments in dark green and Chl b in light green.Figure 3.5 Examples of synthetic approaches to multi‐chromophore arrays: (a) a nine‐porphyrin array unit comprising a central free‐base porphyrin core that acts as final acceptor and is surrounded by eight energy‐donating zinc porphyrins [43]. Source: Choi et al. [41]Figure 3.6 Simplified Z‐scheme of natural oxygenic photosynthesis, showing how two photons are used per electron flowing from the terminal donor (H₂O) to the terminal

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