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selected area electron diffraction (SAED) pattern of petal region. (e) High‐resolution transmission electron microscopy (HRTEM) of petal region. (f) Formate yields of HA‐Co₃O₄ under PEC and EC under different negative potentials. Crystallographic modeling of Co₃O₄ (g) {12

}, (h) {001}, (i) {110}, and (j) {111} facets with side view (left) and oblique view (right). Blue, light blue, and red spheres represent Co³⁺, Co²⁺, and O²⁻, respectively. Source: Huang et al. [54]. © 2013, American Chemical Society.Figure 10.3 (a) Linear sweep voltammetry of the BCN_3.0 electrodes loaded with or not loaded with cocatalysts. (b) Products analyses of photoelectrochemical reduction of CO₂ over cocatalyst‐loaded BCN_3.0 electrodes. Source: Sagara et al. [26]. © 2016, Elsevier.Figure 10.4 Periodic table depicting the primary reduction products in CO₂‐saturated aqueous electrolytes on metal and carbon electrodes. Source: White et al. [2]. © 2015, American Chemical Society.Figure 10.5 Schematic representations for (a) Co^II complex and (b) Fe^II complex for PEC reduction of CO₂. Source: Chen et al. [83]. © 2015, American Chemical Society.Figure 10.6 Schematic of (a) the ruthenium dye‐sensitized TiO₂ nanoparticles with adsorbed CODH enzyme, which catalyzes the reduction of CO₂ to CO. Source: Woolerton et al. [89]. © 2010, American Chemical SocietyFigure 10.7 Schematic image of (a) NiO–RuRe as photocathode and CoO_x/TaON as photoanode. Source: Sahara et al. [30]. © 2016, American Chemical Society.

10 Chapter 11Figure 11.1 (a) Schematic illustrations of different pathways for N₂ reduction, including the dissociative pathway, associative alternating pathway, and associative distal pathway. Source: (a) Shipman et al. [13]. © 2017, Elsevier.Figure 11.2 (a) Schematic of the plasmon excitation‐based photocatalytic N₂ reduction. (b) TEM image of the Au/TiO₂−OV NSs. (c) EPR spectra of four catalysts of TiO₂, TiO₂−OV, Au/TiO₂, and Au/TiO₂−OV. (d) Detected NH₃ concentrations of four catalysts. Source: (a–d) Adapted from Yang et al. [30]. © 2018, American Chemical Society.Figure 11.3 (a) Schematic of the synthesis process of engineering NVs into g‐C₃N₄. (b) ESR and (c) TPD spectra of the prepared g‐C₃N₄ and V−g‐C₃N₄. Source: (a–c) Adapted from Dong et al. [43]. © 2015, Royal Society of Chemistry.Figure 11.4 (a) Schematic photocatalytic N₂ reduction on ultrathin MWO‐1 nanowires. Adsorption configurations of N₂ molecules with different charge dispersions on (b) defect‐rich W₁₈O₄₉, and (c) Mo‐doped W₁₈O₄₉. (d) O K‐edge XAS spectra of different photocatalysts. (e) Schematic of the PCET process for photocatalytic N₂ fixation. (f) Photocatalytic NH₃ yield rates with MWO-1. Source: (a–f) Adapted from Zhang et al. [53]. © 2018, American Chemical Society.Figure 11.5 (a) and (b) HAADF−STEM images and (c) EDX mapping of A‐SmOCl. (d) ESR signals and (e) O K‐edge XAS spectra of different photocatalysts. (f) In situ DRIFT spectra recorded in the N₂ reduction process. Source: (a–f) Hou et al. [61]. © 2019, Elsevier.Figure 11.6 (a) SEM and (b) TEM images of the GaN NWs. (c) TEM image of Ru (5 wt%) decorated GaN NWs. Inset: the diameter distributions of Ru nanoclusters. (d) Schematic of the Schottky barrier between Ru clusters and n‐type GaN NWs. (e) Schematic illustration for the InGaN/GaN with five segments of InGaN on the template of GaN nanowire. (f) NH₃ evolution rates of various photocatalysts under visible‐light illumination. Source: (a–f) Li et al. [74]. © 2017, John Wiley & Sons.Figure 11.7 (a) Schematic illustration of photocatalytic cell for N₂ fixation. (b) and (c) HRTEM images of hollow Au–Ag₂O, the inset is the corresponding FFT of the nanoparticle. (d) NH₃ yields and solar‐to‐ammonia (STA) efficiencies of different photocatalysts. (e) NH₃ yields of Au–Ag₂O under various operating conditions. Source: (a–e) Nazemi et al. [82]. © 2019, Elsevier.Figure 11.8 (a) Schematic of N₂ reduction on the aerophilic–hydrophilic interface. (b) Droplet shapes of the liquid and N₂ bubble on different interfaces. (c) Interfacial water molecule spectra on the surface of Au-PTFE/TS . (d) NH₃ yield rates and FEs on Au/TS and Au−PTFE/TS at different potentials. Source: (a–d) Zheng et al. [89]. © 2019, Elsevier.Figure 11.9 (a) Schematic of the synthesis steps for the Au/end−CeO₂ heterojunction. (b) HAADF−STEM image and the related elemental mapping. Mechanism for N₂ photo‐fixation on the Au/end−CeO₂ heterojunction. The hot carrier separation behaviors on (c) the Au/end−CeO₂ and (d) the core@shell nanostructures. Source: (a–d) Jia et al. [111]. © 2019, American Chemical Society.Figure 11.10 (a) Schematic of TiO_2−xH_y/Fe catalyst for dual‐temperature‐zone photo‐thermal NH₃ synthesis. (b) High‐resolution STEM image of TiO_2−xH_y/Fe catalyst. (c) Steady‐state non‐equilibrium temperature distribution and dual‐temperature‐zone NH₃ synthesis on TiO_2−xH_y/Fe. (d) LTDs between hot Fe and cooling TiO_2−xH_y. (e) SERS mapping of the spatial dispersion of TiO_2−xH_y, Fe, and the adonitol and the detected local LTD. (f) The NH₃ concentrations produced at different apparent catalyst temperatures. (g) Successive light‐on/off measurement of photo‐thermal NH₃ synthesis. (h) The impressive equilibrium‐beyond reactivity of TiO_2−xH_y/Fe at different pressures. Source: (a–h) Mao et al. [118]. © 2019, Elsevier.Figure 11.11 (a) HRTEM, (b) elemental mapping, and (c) HAADF−STEM images of Mo−PCN. (d) Time‐resolved fluorescence kinetics. (e) LT−FTIR spectra for N₂ adsorption. (f) Charge density difference of Mo−PCN with adsorbed N₂. Source: (a–f) Guo et al. [119]. © 2019, Royal Society of Chemistry.Figure 11.12 (a) Schemcatic of designed Mo₂Fe₆S₈−Sn₂S₆ biomimetic chalcogel. Source: (a) Adapted from Banerjee et al. [122]. © 2015, American Chemical Society.

11 Chapter 12Figure 12.1 (a) UV–vis DRS and (b) N₂ adsorption isotherms at 77 K for MIL‐125‐NH₂ and NiO/MIL‐125‐NH₂. Source: Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.2 Ni K‐edge (a) XAFS and (b) FT‐EXAFS spectra of NiO/MIL‐125‐NH₂. Source: Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.3 (a) TEM image, (b) HAADF‐STEM image, and (c‐f) EDX mappings of NiO/MIL‐125‐NH₂. Source: Reproduced with permission from Isaka et al. [24].Figure 12.4 (a) Time course of photocatalytic H₂O₂ production catalyzed by MIL‐125‐NH₂ in the presence and absence of TEOA and visible‐light irradiation (λ > 420 nm). (b) Time courses of photocatalytic H₂O₂ production catalyzed by MIL‐125‐NH₂, NiO/MIL‐125‐NH₂, and Pt/MIL‐125‐NH₂. Source: (a) Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.5 (a) Time course of TEOA oxidation product formation under visible‐light (λ > 420 nm) irradiation for MIL‐125‐NH₂. (b) Mass spectrum of the peak after photoirradiation. (c,d) Reported oxidation products of TEOA in literatures. (e) Plausible product of TEOA oxidation. Source: Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.6 Time courses of H₂O₂ and benzaldehyde production of (a) MIL‐125‐NH₂ and (b) NiO/MIL‐125‐NH₂ dispersed in an acetonitrile solution of benzyl alcohol under visible‐light irradiation (λ > 420 nm). Source: Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.7 Time courses of H₂O₂ (15 mM) decomposition dissolved in 5.0 ml of acetonitrile suspension of 5.0 mg of MIL‐125‐NH₂ and NiO/MIL‐125‐NH₂ at 313 K. Source: Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.8 EPR spectral of suspensions containing DMPO and (a) MIL‐125‐NH₂ or (b) NiO/MIL‐125‐NH₂ under visible‐light irradiation (λ > 420 nm). Source: (a) Isaka et al. [24]. © 2018, Royal Society of Chemistry.Figure 12.9 (a) Digital photographs of two‐phase systems composed of an aqueous phase and a benzyl alcohol phase containing MIL‐125‐NH₂ (left) and MIL‐125‐Rn (n = 4 and 7, right). (b) Photocatalytic H₂O₂ production in the two‐phase system. Source: Isaka et al. [28]. © 2019, John Wiley & Sons.Figure 12.10 (a) XRD patterns and (b) UV–vis DRS for MIL‐125‐NH₂, MIL‐125‐R4, and MIL‐125‐R7. Source: Isaka et al.

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