Photoelectrochemical water splitting into active hydrogen/oxygen species coupling with hydrogenation/oxidation process using layered double hydroxides-based nanocatalysts

doi:10.11949/0438-1157.20200693

Abstract

Abstract:

Hydrogenation/oxidation processes are regarded as the most widely used catalytic reactions in modern chemical development. However, the traditional reaction process always requires harsh reaction conditions (such as high temperature, high pressure, a lot of hydrogen/oxygen consumption, etc), the high cost, overconsumption of energy and low selectivity is always limiting its further development. Therefore, conducting the hydrogenation/oxidation reaction efficiently under mild conditions is one of the greatest challenges in this field. Photoelectrocatalysis has been widely studied due to its wide, clean and sustainable energy sources, which combines the advantages of both photocatalysis and electrocatalysis. Moreover, the process of generating H₂/O₂ by photoelectrocatalytic water splitting involves the production of highly reactive intermediate species (active hydrogen *H and active oxygen *O) which can be used by directly coupling the hydrogenation/oxidation catalytic processes, and the efficiency of coupled reaction will be greatly improved. The review here summarizes the research progress of photoelectrocatalysis from three aspects: active species of intermediate products produced by photoelectrochemical water splitting, hydrogenation/oxidation reaction of the traditional chemical industry, and coupling photoelectrochemical water splitting with hydrogenation/oxidation process using layered double hydroxides (LDHs)-based nanomaterials. It is expected to provide ideas for the high selectivity and low cost preparation of high value-added organic chemicals.

Key words: catalyst, photochemistry, electrochemistry, hydrogenation/oxidation processes, layered double hydroxides

摘要：

加氢/氧化催化是现代化学工业中最广泛的催化过程，传统加氢/氧化催化需要高温高压、消耗大量氢气/氧气（或双氧水等），且存在高成本、高能耗、低选择性等问题。因此，如何在温和条件下绿色高效地实现加氢还原/氧化反应，是目前催化领域的研究热点和难点之一。光电催化过程因其能量来源广泛、清洁环保，且结合了光催化和电催化的优势，已成为当前研究热点，而光电分解水产生H₂/O₂过程涉及高反应活性的中间物种（活性氢*H、活性氧*O）的产生。利用光电解水产生的中间*H/*O物种，并使其直接参与加氢/氧化催化过程，实现一步光电解水制活性氢/氧耦合加氢/氧化过程，有望极大提高反应的效率。通过对催化剂结构进行调控，使得耦合过程可在温和的反应条件下进行，同时可避免因使用氢气/氧气等导致的安全和耗能等问题。本文综述了光电分解水过程，传统化工的加氢/氧化过程以及光电分解水与加氢/氧化耦合反应等方面的发展，介绍了水滑石基纳米材料在光电解水耦合加氢/氧化过程中的结构和性能优势，并对未来研究方向进行了展望，以期为高附加值有机化学品的高选择性低成本制备提供思路。

关键词: 催化剂, 光化学, 电化学, 加氢/氧化过程, 水滑石

CLC Number:

TQ 139.2

Tianyi LAI,Jikang WANG,Tian LI,Sha BAI,Xiaojie HAO,Yufei ZHAO,Xue DUAN. Photoelectrochemical water splitting into active hydrogen/oxygen species coupling with hydrogenation/oxidation process using layered double hydroxides-based nanocatalysts[J]. CIESC Journal, 2020, 71(10): 4327-4349.

来天艺,王纪康,李天,白莎,郝晓杰,赵宇飞,段雪. 光电解水产活性氢/氧耦合加氢/氧化过程用水滑石基纳米材料[J]. 化工学报, 2020, 71(10): 4327-4349.

Figures/Tables 17

Fig.1 Schematic illustration of LDHs(a)[17]; Conduction band and valence band potentials of some common LDH materials versus NHE at pH 7 (b)[22]

Fig.2 A polyhedral representation of the ZnTi-LDH structure (a); H2 evolution productivity of MTi-LDH (b); ESR spectra recorded for DMPO-·O2- in methanol dispersion (c)[29]; Proposed structural model of energy states for the Ti3+ self-doped NiTi-LDH and schematic illustration of the O2 evolution process over the NiTi-LDH nanosheet under visible-light irradiation (d); Fluorescence spectra (e); O2 evolution from aqueous solution using 10-2 mol·L-1 AgNO3 as the sacrificial acceptor under visible-light using NiTi-LDH with different thickness (f)[30]

Fig.3 Schematic illustration for the preparation of Cu2O@ZnCr-LDH hollow coreshell photocatalyst(a); Rate of gas generation as function of irradiation time (b); Schematic illustration for the photoexcited electron separation/transport in the Cu2O@ZnCr-LDH system (c)[33]; Gas generation rate (d); Schematic definition for S- and W-parameters in CDB-PAS measurements of Cu2O@ZnCr-LDH (e)[34]

Fig.4 Schematic illustration of introducing oxygen vacancy defects to NiFe-LDH nanoarray electrode (a); Linear sweep voltammetry polarization curves of as-prepared NiFe-LDH after NaBH4 treatment (b); Free energy plots calculated results of OER process NiFe-LDHs treated by NaBH4 (c)[39]; CoFe-LDH nanosheets by Ar plasma exfoliation (d)； LSV curves of bulk CoFe-LDHs and ultrathin CoFe-LDH nanosheets (e); Magnitude of the k3-weighted Fourier transforms of the Fe edge XANES spectra for bulk CoFe-LDH and ultrathin CoFe-LDH (f)[9]

Fig.5 Schematic illustration for the synthesis of CoNiP@NiFe-LDH hierarchical arrays (a); Photographs of water-splitting system (b); LSV results of two-electrode cell assembled by various materials (c)[44]; The *H Gibbs free energy of different catalysts (d)[48]

Fig.6 Schematic illustration for the fabrication of TiO2/ZnFe-LDH-PE NAs (a); J-V curves (b); Schematic illustration for the PEC water oxidation process over the TiO2/ZnFe-LDH photoanode (c)[50]； Schematic illustration of the fabrication of ZnO@ CoNi-LDH core-shell NWs array(d); IPCE for ZnO@LDH electrode with various LDH deposition time (e); Schematic illustration of the photoelectrochemical water oxidation process by the as-obtained ZnO@ CoNi-LDH core-shell NWs array (f)[53]

Fig.7 Scheme of energy levels and charge transfer pathways of C3N4 and MMO@C3N4(a); The light-driven H2O2 generation in O2-equilibrated conditions over MMO@C3N4, Ni@C3N4, Fe@C3N4, and MMO/C3N4-Mix (b)[60]; The light-driven H2O2 generation (c); H2O2 decomposition over TiO2-ZnTiO3, ZnTi-MMO and P25 (d)[61]

Fig.8 Alcohols STY at different pressures over catalysts with four Cu/Fe ratios (1/1, 2/1, 4/1, and 6/1)(a); CO-TPD profiles of Fe1, Cu4, and CuxFey samples (b)[69]; ESR spectrum over Ni-NiO structure (c)[70]; The potential energy profiles for CO2 formation, C2H4 adsorption, and hydrogenation under excited states on Fe3O4, 4O/Fe, and 4O/Fe3Zn (d); Fabrication of Co-x catalysts by H2 reduction of ZnCoAl-LDH nanosheets at 300—700℃ (e)[71]

Fig.9 Schematic illustration of the morphological evolution process of the as-obtained flower-like hierarchical LDH microspheres(a); N2-sorption isotherms and pore size distribution (inset) of MgFe-LDH microspheres with different inner architecture (b); Cyclic voltammograms at the MgFe-LDH microspheres modified electrodes (c)[76]; Design schematic of the Au-NCs/LDH catalyst (d)[77]; Time course for the dehydrogenation of benzyl alcohol over Au/HT catalyst prepared by the DP method (e)[78]

Fig.10 Water splitting combined with hydrogenation/oxidation for the synthesize of high-valuable fine chemicals

Fig.11 Selectivity of CH4, CO, and H2 in CO2PR on monolayer NiAl-LDH under different wavelength (a); Illustration for the species of defects on monolayer NiAl-LDH. VM represents metal defect (M=Ni, Al), VOH represents the hydroxyl defect (b); The energy levels for the singlet and triplet excited states of photosensitizer Ru(bpy)3Cl2, together with the band edge placements for the CBM, defect state, and valence band minimum (VBM) of monolayer NiAl-LDH (VNi&OH) versus the normal hydrogen electrode (NHE) (c)[86]; Illustration of sulfur vacancy-promoted selective synthesis of functionalized aminoarenes via transfer hydrogenation of nitroarenes with H2O as the hydrogen source over a cobalt sulfide nanosheet cathode (d)[87]; Illustration of selective transfer semihydrogenation of alkynes with H2O (D2O) as the H (D) source over a Pd-P cathode (e)[88]

Fig.12 Schematic illustration of defect-containing NiO derived from the topological transformation of NiAl-LDH(a); The corresponding k3-weighted FT spectra of NiO, NiAl-x, and NiAl-LDH (b); Selectivity of NiAl-275 under different monochromatic light (c)[89]

Fig.13 Room-temperature photoluminescence (PL) spectra of CoFe-LDH and NiCoFe-LDH (a); Selectivity of CH4, CO, and H2 under irradiation above 500 nm for CoFe-LDH and NiCoFe-LDH (b)[90]; UV-vis spectra for the various u-MAl-LDH photocatalysts (c); Production rates of CO, H2, and CH4 on various u-MAl-LDH photocatalysts in CO2PR under visible light (d)[91]

Fig.14 Schematic illustration of photocatalytic CO2 reduction to tunable syngas on CoAl-LDH/MoS2 heterostructures with different catalyst concentrations (a); LDH/MoS2 nanocomposite yield and selectivity of CO and H2 in CO2PR with different concentrations (b)[94]; Schematic diagram of the selectivity of photocatalytic CO2 reduction by different anion intercalated NiAl-LDH (c)[95]; Selectivity of LDH and Ce-x (d)[96]

Fig.15 Comparison of reaction rate between PEC catalysis in this work and photocatalysis reported previously (the Ref. numbers in the figure were Ref. numbers of the Ref.[97])(a); DMPO spin-trapping ESR spectra recorded for DMPO-·O2- over TiO2, TiO2/C, and TiO2/C/Co3O4 sample, respectively (b); Schematic illustration for the PEC WS-OR coupling process (c)[97]; Photocurrent-potential curves under illumination of urea oxidation (d)[98]

Fig.16 Supercell model of ZnTi-LDH layer doped with VO vacancies(a); Schematic band diagrams (b); Reaction time profiles of phenol (c); Conversion of benzene oxidation (d)； 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as spin-trapping agent under UV-vis light irradiation to detect ·OH (e) and·O2- (f), respectively[99]

Fig.17 HMF oxidation process and products(a); Schematic diagram of the electrochemical system used for the overall cell reactions (b); Concentration changes of HMF and its oxidation products with the time of chronoamperometric tests (c); LSV curves of the NiFe-LDH nanosheet growth on carbon fiber paper (d)[102]

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