光催化CO2还原的超薄层状催化剂

doi:10.3866/PKU.WHXB202005027

Abstract

Abstract:

The acceleration of industrialization and the continuous upgradation of consumption structure has increased the atmospheric content of CO₂ far beyond the past levels, leading to a serious global environmental problem. Photocatalytic reduction of CO₂ is one of the most promising methods to solve the problem of rising atmospheric CO₂ content. The core of this technology is to develop efficient, environment-friendly, and affordable photocatalysts. A photocatalyst is a semiconductor that can absorb photons from sunlight and produce electron-hole pairs to initiate a redox reaction. Owing to their low specific surface areas, significant electron-hole recombination, and less surface-active sites, bulk photocatalysts are not satisfactory. Ultrathin layered materials have shown great potential for photocatalytic CO₂ reduction owing to their characteristics of large specific surface area, a large number of low-coordination surface atoms, short transfer distance from the inside to the catalyst surface, along with other advantages. Photoexcited electrons only need to cover a short distance to transfer to the nanowafer surface, and the speed of migrating electrons on the nanowafer surface is much higher than that in the layers or in the bulk catalyst. The ultrathin structure leads to significant coordinative unsaturation and even vacancy defects in the lattice structure of the atoms; while the former can be used as active sites for CO₂ adsorption and reaction, the latter can improve the separation of the electron-hole pair. This review summarizes the latest developments in ultrathin layered photocatalysts for CO₂ reduction. First, the photocatalytic reduction mechanism of CO₂ is introduced briefly, and the factors governing product selectivity are explained. Second, the existing catalysts, such as g-C₃N₄, black phosphorus (BP), graphene oxide (GO), metal oxide, transition metal dichalcogenides (TMDCs), perovskite, BiOX (X = Cl, Br, I), layered double hydroxide (LDH), 2D-MOF, MXene, and two-dimensional honeycomb-like Ge―Si alloy compounds (gersiloxenes), are classified. In addition, the prevalent preparation methods are summarized, including mechanical stripping, gas stripping, liquid stripping, chemical etching, chemical vapor deposition (CVD), template method, self-assembly of surfactant, and the intermediate precursor method of lamellar Bi-oleate complex. Finally, we introduced the strategy of improving photocatalyst performance on the premise of maintaining its layered structure, including the factors of thickness adjustment, doping, structural defects, composite, etc. The future opportunities and challenges of ultrathin layered photocatalysts for the reduction of carbon dioxide have also been proposed.

Key words: Photocatalysis, Carbon dioxide, Ultra-thin, Layered, Nanosheets

Zuzeng Qin, Jing Wu, Bin Li, Tongming Su, Hongbing Ji. Ultrathin Layered Catalyst for Photocatalytic Reduction of CO₂[J]. Acta Phys. -Chim. Sin. 2021, 37(5), 2005027. doi: 10.3866/PKU.WHXB202005027

Figures/Tables 16

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Table 1

Preparation, modification methods, photocatalytic activity test conditions, and product yield of ultrathin layered catalyst for photocatalytic CO2 reduction"

Photocatalyst species	Preparation method	Sacrificial agent	Reaction phase state	Light source	Product	Catalyst dosage (mg)	Yield (μmol∙h⁻¹)	Ref
g-C₃N₄	Annealed at 550 ℃		G-S	300 W Xe lamp	CH₄	20	0.10	35
S@g-C₃N₄	Using thiourea instead of melamine as raw material		G-S	300 W Xe lamp	CH₃OH	100	0.037	114
(V_N)g-C₃N₄	Post-treatment with 3% hydrogen argon at 550 ℃ in a tubular furnace		G-S	500 W Xe lamp, 400 nm filter	CH₄		1.16 (g⁻¹)	118
0D/2D BP/g-C₃N₄	Mechanical mixing		G-S	300 W Xe lamp	CO	30	0.20	45
2D/2D g-C₃N₄/NiAl-LDH	In situ hydrothermal synthesis of NiAl-LDH on g-C₃N₄		G-S	300 W Xe lamp, 420 nm filter	CO	50	0.41	128
(V_O)ZnAl-(LDH)	Reverse micelle method		G-S	300 W Xe lamp	CO	100	0.76	21
(V_O)TiO₂QDs/g-C₃N₄	In situ pyrolysis of mixture of melamine and NH₂-MIL-125 (Ti)	TEOA	G-L-S	300 W Xe lamp, 400 nm filter	CO	5	0.47	122
0D/2D B₄C/TiO₂	In situ formation of TiO₂ on B₄C by solvothermal addition		G-S	300 W Xe lamp	CH₄	6	0.025	51
0D/2D Cu/TiO₂	In situ online synchronous photo deposition		G-L-S	300 W Xe lamp	CO	100	0.16	125
2D/2D SnS₂/TiO₂	In situ hydrothermal synthesis of SnS₂ on TiO₂		G-S	300 W Xe lamp	CH₄	100	2.3	130
GO	Use mild oxidant H₃PO₄ instead of H₂SO₄		G-S	300 W Halogen lamp	CH₃OH	200	0.030	50
MEA-ZnO	Amino functionalization of monoethanolamine by hydrothermal method		G-S	300 W Xe lamp	CO	20	0.13	52
0D/2D Cu₂O/WO₃-001	Electrodeposition of Cu₂O on the surface of WO₃		G-S	300 W Xe lamp, (400 nm filter)	CO	85	0.49	53
Co₃O₄(Adding photosensitizer)	Calcination of Co-MOF nano tablets as precursors	TEOA	G-L-S	5 W LED lamp	CO	7.5	4.5	54
Bi₂WO₆	Intermediate precursor method of lamellar Bi-oleate complex		G-L-S	300 W Xe lamp, AM 1.5G filter	CH₃OH	200	15	106
Bi₂MoO₆	Solvothermal method		G-L-S	13 W LED lamp	C₂H₅OH	50	1.7	57
Co@BiVO₄	In situ doping, self-assembly of surfactant (CTAB)		G-S	25 W Ultraviolet lamp	CH₄	30	0.69	112
(V_V)BiVO₄	Self-assembly of surfactant (CTAB), Lower reaction temperature and longer reaction time		G-L-S	300 W Xe lamp, AM 1.5 filter	CH₃OH	200	79.66	120
Sr₃Ti_(2−x−y)Fe_xSO_(7−z)N_z	In situ doping of Fe₂O₃ and thiourea	NaOH	G-L-S	77 W Mercury lamp	CH₃OH	400	24	58
Ag/BaLa₄Ti₄O₁₅	Ag loaded as cocatalyst		G-L-S	400 W Mercury lamp	CO	300	22	59
BiOCl	Self-assembly of surfactant (CTAB)		G-L-S	500 W Xe lamp	CH₄	100	0.15	64
(V_O)BiOBr	Solvothermal method of glycol instead of water		G-S	500 W Xe lamp, AM 1.5 filter	CH₄		0.96 (g⁻¹)	67
Bi₄O₅Br₂-UN	Self-assembly of surfactant (CTAB)		G-S	300 W Xe lamp	CO	20	0.63	110
0D/2D Ag/2H-MoS₂	Phase transformation in o-dichlorobenzene after liquid flaking, then loading Ag particles by chemical reduction		G-L-S	250 W Mercury lamp	CH₃OH	20	7.3	69
Partial oxidation SnS₂	Solvothermal method of glycol replacing one sixth of water		G-S	300 W Xe lamp, AM 1.5 filter, 420 nm filter	CO	100	1.2	70
Zn-MOF(Adding photosensitizer)	Solvothermal method	TEOA	G-L-S	300 W Xe lamp, 420 nm filter	CO	10	133.8	79
HGeSiOH	Accomplished by the typical topotactic deintercalation of the Zintl-phase precursor in −30 ℃ hydrochloric acid	NaSO₃	G-L-S	300 W Xe lamp	CO	60	0.41	84

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References 130

1	Vergara J. ; McKesson C. ; Walczak M. Energy Policy 2012, 49, 333. doi: 10.1016/j.enpol.2012.06.026
2	Zhao Y. ; Liu Z. Chin. J. Chem. 2018, 36 (5), 455. doi: 10.1002/cjoc.201800014
3	Steinlechner C. ; Junge H. Angew. Chem. Int. Edit. 2018, 57 (1), 44. doi: 10.1002/anie.201709032
4	Guo S. H. ; Zhou J. ; Zhao X. ; Sun C. Y. ; You S. Q. ; Wang X. L. ; Su Z. M. J. Catal. 2019, 369, 201. doi: 10.1016/j.jcat.2018.11.004
5	Li A. ; Wang T. ; Li C. ; Huang Z. ; Luo Z. ; Gong J. Angew. Chem. Int. Edit. 2019, 58 (12), 3804. doi: 10.1002/anie.201812773
6	Zhou B. ; Song J. ; Xie C. ; Chen C. ; Qian Q. ; Han B. ACS Sustain. Chem. Eng. 2018, 6 (5), 5754. doi: 10.1021/acssuschemeng.8b00956
7	Ye J. ; He J. ; Wang S. ; Zhou X. ; Zhang Y. ; Liu G. ; Yang Y. Sep. Purif. Technol. 2019, 220, 8. doi: 10.1016/j.seppur.2019.03.042

Ultrathin Layered Catalyst for Photocatalytic Reduction of CO₂

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Ultrathin Layered Catalyst for Photocatalytic Reduction of CO2

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Ultrathin Layered Catalyst for Photocatalytic Reduction of CO₂