Research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts

doi:10.1016/S1872-2067(20)63714-7

Abstract

Abstract:

With the increasing concerns to energy shortage and environmental problems in modern society, the development of cheap, clean, and sustainable energy alternatives has been attracting tremendous attention globally. Among various strategies of renewable energy exploration, solar-driven water splitting into its compositional elements H₂ and O₂ is an ideal approach to convert and store renewable solar energy into chemical bonds. In recent few decades, as an emerging new type of catalysts, polyoxometalates (POMs) have been widely utilized for water splitting due to their versatile synthetic methodology and highly tunable physicochemical and photochemical properties. This critical review addresses the research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts, including plenary POMs, transition-metal-substituted POMs, POM@MOF composites, and POM-semiconductor hybrids, under UV, near UV and visible light irradiation. In addition, the catalytic mechanism for each reaction system has been thoroughly discussed and summarized. Finally, a comprehensive outlook of this research area is also prospected.

Key words: Polyoxometalates, Light-driven hydrogen evolution, POM@MOF composites, POM-semiconductor hybrids, Catalytic mechanism

Mo Zhang, Huijie Li, Junhao Zhang, Hongjin Lv, Guo-Yu Yang. Research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts[J]. Chinese Journal of Catalysis, 2021, 42(6): 855-871.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63714-7

https://www.cjcatal.com/EN/Y2021/V42/I6/855

Figures/Tables 30

Fig. 1. A schematic illustration for artificial photosynthesis: an antenna light-absorption and charge separating structure interfaced with catalysts.

Fig. 2. Various potential applications of polyoxometalates.

Scheme 1. Timeline of representative breakthroughs of POM-based photocatalysts for light-driven hydrogen evolution reaction.

Fig. 3. X-ray crystal structures of polyoxometalates in combined ball-and-stick and polyhedral representations. blue: W; green: Nb; yellow: Ta; orange: V; light blue: transition metals; Pink: P; grey: K; Red: O.

Fig. 4. The mechanistic illustration of hydrogen production using semiconductor photocatalyst.

Table 1 Summary of catalytic H2 production using POM photocatalysts under UV or near UV light.

Catalyst	Light source	Photosensitizer	Sacrificial agent	Cocatalyst	Activity (µmol h^-1 g^-1)	Ref.
{MSiW₁₁} (M=Ni, Cu, Co, Zn)	500 W Xe lamp	None	Zn powder	Pt	150, 98, 65, 48	[67]
{MTiW₁₁} (M = Fe, Co, Zn)	simulated solar light (350-760 nm)	None	polyvinyl alcohol	None	500, 484, 294	[68]
{Ta₁₂}	(250 W Hg) ultraviolet irradiation	None	CH₃OH	Pt	1250	[75]
{Ta₁₆}	(250 W Hg) ultraviolet irradiation	None	CH₃OH	Pt	803	[75]
{Ta₁₈P₁₂W₉₀}	(500 W Hg) ultraviolet irradiation	None	CH₃OH	None	8301.32	[76]
{Yb₂Ta₁₈P₁₂W₉₀}	(500 W Hg) ultraviolet irradiation	None	CH₃OH	None	6494.4	[76]
{CrTa₆Si₂W₁₈}	(500 W Hg) ultraviolet irradiation	None	CH₃OH	None	1001.7	[77]
{FeTa₆Si₂W₁₈}	(300 W Hg) ultraviolet irradiation	None	CH₃OH	None	743.8	[77]
{Cr₃[Ta₃P₂W₁₅]₂}	(500 W Xe)	None	CH₃OH	H₂PtCl₆	198.3	[78]
{Cr₄[Ta₃P₂W₁₅]₄}	(500 W Xe)	None	CH₃OH	H₂PtCl₆	89.2	[78]
{[Nb₂O₂][SiNb₁₂]}	300 W Xe lamp	None	CH₃OH	Pt	2100	[81]
{Nb₂₄}	(500 W Hg) ultraviolet irradiation	None	TEOA	Cobaloximes	5193.87	[82]
{Nb₃₂}	(500 W Hg) ultraviolet irradiation	None	TEOA	Cobaloximes	5056.43	[82]
{Nb₉₆}	(500 W Hg) ultraviolet irradiation	None	TEOA	Cobaloximes	4714.7	[82]
{Nb₄₈}	300 W Xe lamp	None	TEA	Cobaloximes	13.9	[83]
{PNb₁₂V₆-1}	300 W Xe lamp	None	CH₃OH	0.75% Pt	10.31	[84]
{PNb₁₂V₆-2}	300 W Xe lamp	None	CH₃OH	0.75% Pt	10.45	[84]
{Nb₄O₆(SiW₉Nb₃)₄}	150 W Hg ultraviolet irradiation	None	CH₃OH	Pt	1284.12	[87]
{TeNb₅}	300 W Xe lamp	None	CH₃OH	Te	776	[88]
{Sn₄Si₂W₁₈}	300 W Xe > 420 nm	None	CH₃OH	H₂PtCl₆	4.62	[90]
{Fe₆Se₆W₃₄}	500 W Hg lamp	None	CH₃OH	None	1422.5	[91]
{Fe₁₀Se₈W₆₂}	500 W Hg lamp	None	CH₃OH	None	900.8	[91]

Fig. 5. Schematic diagram and time courses of photocatalytic H2 evolution by {MTiW11} (M = Fe, Co, Zn) under simulated sunlight. Adapted with permission from Ref. [68]. Copyright 2014 Royal Society of Chemistry.

Fig. 6. X-ray crystal structures of {Ta12} and {Ta16} and the schematic mechanism of photocatalytic hydrogen production. Adapted with permission from Ref. [75]. Copyright 2012 American Chemical Society.

Fig. 7. Schematic diagram of photocatalytic H2 and O2 evolution by photocatalyst {[Nb2O2][SiNb12]} under UV irradiation. Adapted with permission from Ref. [81]. Copyright 2011 American Chemical Society.

Fig. 8. The solid-state emission spectra of {PNb12V6-1} (a) and {PNb12V6-2} (b) at room temperature; the experimental (red) and simulated (black) PXRD patterns of {PNb12V6-1} (c) and {PNb12V6-2} (d); XRD patterns of photocatalysts {PNb12V6-1} (c) and {PNb12V6-2} (d) after photocatalytic water splitting reaction under 125 W Hg lamp (green) and 300 W Xe lamp (blue) irradiation. Adapted with permission from Ref. [84]. Copyright 2014 Royal Society of Chemistry.

Fig. 10. Polyhedral model of {CrNb9}, {MnNb9}, and {CoNb9} clusters, and H2-evolution upon Xe-lamp irradiation of 0.2 g of TM-substituted decaniobate TMA salts in 50 mL MeOH-H2O solution (20% v/v). Adapted with permission from Ref. [89]. Copyright 2014 Royal Society of Chemistry.

Fig. 11. Polyhedral model of {Fe6Se6W34}, {Fe10Se8W62} clusters, and the time course of H2 evolution from 100 mg of photocatalysts (a) {Se4W36}, (b) {Fe6Se6W34}, and (c) {Fe10Se8W62} under 500 W mercury lamp irradiation in methanol/H2O (1/5, v/v). Adapted with permission from Ref. [91]. Copyright 2014 Royal Society of Chemistry.

Scheme 2 Schematic diagram of photocatalytic H2 evolution using POM-based photocatalyst under UV- light irradiation.

Scheme 3. Schematic “Z scheme” mechanism of photocatalytic H2 evolution using POM-based photocatalysts under simulated solar light irradiation. D means electron donor.

Table 2 Overview of POM-catalyzed water reduction reactions under visible light.

Catalyst	Photosensitizer	Sacrificial agent	Co-catalyst	TON/TOF (s^-1)	Time (h)	Ref.
{AlSiW₁₁}	Eosin Y	TEOA	Pt	12.5/7	20	[94]
{CoCoW₁₁}	Eosin Y	TEOA	Pt	100/7×10^-6	2.3	[95]
{D_Si[Ir]}	None	NEt₃	None	41/69.4×10^-6	168	[96]
{Mn₄V₂}	[Ru(bpy)₃]²⁺	TEOA	None	42/—	5.5	[46]
{Ni₄P₂}	[Ir(ppy)₂(dtbbpy)]⁺	TEOA	None	290/—	2.5	[47]
{Ni₁₆As₄P₄}	[Ir(ppy)₂(dtbbpy)]⁺	TEOA	None	360/—	5	[48]
{Cu₄P₂}	[Ir(ppy)₂(dtbbpy)]⁺	TEOA	None	1270/—	5	[49]
{Co₆P₃}	Eosin Y	TEOA	None	—	—	[97]
{NiGeW₁₁}	[Ru(bpy)₃]²⁺	Ascorbic acid	None	36.8/9×10^-3	15	[98]
{[Ni₁₆(B-PW₉O₃₄)₄]}	[Ir(ppy)₂(dtbbpy)]⁺	TEOA	None	931.1/—	12	[99]
{Ni₁₄SiW₉}	[Ir(ppy)₂(dtbbpy)]⁺	TEOA	None	256/2.7×10^-2	4	[100]
{Cu₅Si₂}	[Ir(ppy)₂(dtbbpy)]⁺	TEOA	None	718.9/134.8	6	[101]
{P₂W₁₈@UiO (Ru-derived)}	None	TEOA	None	79/—	14	[109]
{Ni₄P₂@MOF-1 (Ir derived-UiO)}	None	CH₃OH	None	1476/—	72	[110]
{WD-POM@SMOF-1}	[Ru(bpy)₃]²⁺	TEOA	None	392/—	12	[111]
{P₂W₁₅V₃@MIL-101}	[Ru(bpy)₃]²⁺	TEOA	None	56/—	8	[112]
{Cu₂₄-Based POM@ZZULI-1}	Fluorescein	TEOA	None	—	—	[113]
{Ta₆-3/CZS }	None	S^2-/SO₃^2-	None	—	—	[121]

Fig. 13. Molecular representation of different {DSi[Ir]} dyads described in this study. Color code: WO6 octahedra, blue; PO4 tetrahedra, green. Adapted with permission from Ref. [96]. Copyright 2013 Royal Society of Chemistry.

Fig. 14. (a) Proposed mechanism for visible-light-driven hydrogen evolution catalyzed by catalyst {Ni4P2}; (b) Long-term photocatalytic H2 evolution using {Ni4P2} catalyst. Adapted with permission from Ref. [47]. Copyright 2014 American Chemical Society.

Fig. 15. X-ray crystal structures of {[Ni16(A-PW9O34)4]}, {[Ni16(A-PW9O34)2(B-PW9O34)2]}, and {[Ni16(B-PW9O34)4]}, and the schematic diagram of photocatalytic hydrogen production. Adapted with permission from Ref. [99]. Copyright 2017 Elsevier.

Fig. 16. (a) Polyhedral and ball-and-stick representation of the structure of compound {Cu5Si2} and {Ni5Si2}; (b) Visible light-driven HER kinetics of different control experiments. Adapted with permission from Ref. [101]. Copyright 2020 Royal Society of Chemistry.

Scheme 4. Schematic illustration of photocatalytic hydrogen evolution by EY-sensitized POM.

Scheme 5. Schematic illustration of visible-light-induced H2 evolution using [Ru(bpy)3]2+ photosensitizer and POM catalyst.

Fig. 17. (a) A ball-and-stick representation of 1, highlighting the three directional channels in the 3D framework. The three different colored tubes represent the different channels in 1. (b) A topological representation of 2. The channels within which are shown in blue tubes. (c) Channel and ball-and-stick representations of 3. In the pictures, the polyanions are shown in sticks. Adapted with permission from Ref. [108]. Copyright 2012 Wiley.

Fig. 18. One-pot synthesis of the POM@UiO system via charge assisted self-assembly. [P2W18O62]6-, purple polyhedra; Zr, cyan; Ru, gold; N, blue; O, red; C, light gray. Adapted with permission from Ref. [109]. Copyright 2015 American Chemical Society.

Scheme 6. Dual-functionalized mixed Keggin- and Lindqvist-type {CuI24(μ3-Cl)8(μ4-Cl)6}-based POM@MOFs as photocatalysts for both H2 and O2 evolution. Adapted with permission from Ref. [113]. Copyright 2019 American Chemical Society.

Scheme 7. Proposed catalytic cycle for visible-light-driven hydrogen evolution catalyzed by POM@MOF composites.

Fig. 21. (a) The PL emission spectra of TiO2, TiO2-SiNH2, TiO2-Pt and TiO2-SiNH2-PW11Pt2; The LSV graph (b), EIS spectra (c) and transient photocurrent responses (d) of TiO2, TiO2-SiNH2 and TiO2-SiNH2-PW11Pt2. Adapted with permission from Ref. [133]. Copyright 2020 Royal Society of Chemistry.

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