压电极化增强光催化能源转化的研究进展

doi:10.3866/PKU.WHXB202212048

Abstract

Abstract:

Semiconductor-based photocatalysis is an efficient technology that reduces energy consumption and environmental pollution; however, it is impeded by Coulombic attraction-induced charge recombination, which reduces solar conversion efficiency. The internal electric field induced by heterointerface engineering, defect engineering, heteroatom doping, ferroelectric polarization, and polar surface terminations intervening in the uniform charge distribution can drive the directional migration of photogenerated electrons and holes, suppressing the charge recombination and back-reaction of intermediate species. However, the built-in electric field is static and easily shielded by internal active carriers and externally charged ions, which is detrimental to successive charge separation. Moreover, the internal electric field that relies solely on the structural design of the catalyst often requires complex preparation processes and is disqualified from simple and efficient solar energy conversion. By coupling the piezoelectric effect with the photoexcitation feature in piezo-photocatalysis, charge carrier dynamics can be persistently modulated. The noncentrosymmetric structures of piezoelectrics result in the deviation of positive and negative charge centers with the exerted external stress, generating nonzero dipole moments and polarization charges on the opposite terminals of the crystal. On the one hand, the polarized bound charges and initiated piezoelectric polarization field by mechanical stress promote the separation and transfer of photoinduced charges in both the bulk and on the surface of the catalyst, facilitating more active carriers to participate in the surface reaction. On the other hand, the accumulation of piezoelectric polarization charges on the surface contributes to the upward or downward bending of the band, which can flexibly manipulate the charge transfer behavior at the heterojunction interface, further steering the spatial distribution of electrons and holes. In addition, band tilting induced by piezoelectric polarization can also modulate the energy band structure of the catalyst to match the redox potential of the target reaction, breaking the intrinsic thermodynamic restriction. Hence, the coupling of solar and mechanical energy significantly improves the efficiency of catalytic energy conversion. As a complex reaction process of piezo-photocatalysis, diverse enhancement strategies have been implemented; however, there are few systematic and pertinent overviews for high-performance piezo-photocatalyst design. This study introduces the mechanism of piezoelectric polarization-enhanced photocatalysis and summarizes the catalytic enhancement strategy based on the piezo-photocatalysis reaction process, including morphology and polarization regulation, heterostructure construction, and surface engineering. Meanwhile, recent advances in piezo-photocatalysis for energy applications have been reviewed. Finally, the problems and challenges associated with the development of piezo-photocatalysis are analyzed and discussed.

Key words: Polarization, Piezo-photocatalysis, Charge separation, Band bending, Energy conversion

Cheng Hu, Hongwei Huang. Advances in Piezoelectric Polarization Enhanced Photocatalytic Energy Conversion[J]. Acta Phys. -Chim. Sin. 2023, 39(11), 2212048. doi: 10.3866/PKU.WHXB202212048

Figures/Tables 10

Fig 1

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Table 1

Summary of the energy applications of piezo-photocatalysis."

Catalysts	Design strategy	Reaction solution	Reaction conditions	Activities	Ref.
Water Splitting H₂ production
Cd_xZn_1–xS nanorods	Morphology modulation	Lactic acid, 1% (wt) Pt	300 W Xe lamp, 150 W ultrasonic	H₂: 4.45 mmol∙g⁻¹∙h⁻¹	112
Bi_0.5Na_0.5TiO₃	Polarization modulation	Triethanolamine, 1% (wt) Pt	300 W Xe lamp, 150 W ultrasonic	H₂: 158 μmol∙g⁻¹∙h⁻¹	113
CH₃NH₃PbI₃	Polarization modulation	HI solution	500 W tungsten-halogen lamp, 90 W ultrasonic	H₂: 23.30 μmol∙h⁻¹	114
CN nanosheets	Morphology modulation	Glucose	300 W Xe lamp, 280 W ultrasonic	H₂: 12.16 mmol∙g⁻¹∙h⁻¹	115
Cyano groups grafted CN nanosheets	Surface engineering	Na₂SO₃, Pt	300 W Xe lamp, 40 kHz ultrasonic	H₂: 13.53 mmol∙g⁻¹∙h⁻¹	116
CdS nanosheets	Morphology modulation	0.1 mol∙L⁻¹ Na₂S and Na₂SO₃	300 W Xe lamp, 100 W ultrasonic	H₂: 633 μL∙h⁻¹	105
CdS nanorod arrays	Morphology modulation	Pure water	300 W Xe lamp, 100 W ultrasonic	H₂: 20 μL∙h⁻¹	106
La₂NiO₄ nanoplates	Morphology modulation	Pure water	300 W Xe lamp, 100 W ultrasonic	H₂: 1.09 mmol∙g⁻¹∙h⁻¹	107
SrTiO₃	Polarization modulation	CH₃OH, 1% (wt) Pt	300 W Xe lamp, 60 W ultrasonic	H₂: ~70 μmol∙h⁻¹	109
Co-doped MoS₂	Polarization modulation	0.05 mol∙L⁻¹ ammonium borate	50 W NIR light, 200 W ultrasonic	H₂: 1.53 mmol∙g⁻¹∙h⁻¹	111
BaTiO₃@MoSe₂	Heterojunction	CH₃OH solution	150 W Xe lamp, 300 W ultrasonic	H₂: 4.53 mmol∙g⁻¹∙h⁻¹	126
KNbO₃@MoS₂	Heterojunction	Triethanolamine, 1% (wt) Pt	300 W Xe lamp, 110 W ultrasonic	H₂: 96 μmol∙g⁻¹∙h⁻¹	127
Au@MoS₂	Surface engineering	CH₃OH solution	200 W Xe lamp, 300 W ultrasonic	H₂: 2.98 mmol∙g⁻¹∙h⁻¹	117
TiO₂@ZnO	Heterojunction	CH₃OH solution	50 W Xe lamp, 50 W ultrasonic	H₂: 3.05 μmol∙g⁻¹∙h⁻¹	122
ZnO@ZnS@MoS₂	Heterojunction	5 mmol∙L⁻¹ Na₂S and Na₂SO₃	100 W Xe lamp, 200 W ultrasonic	H₂: 10.42 mmol∙g⁻¹∙h⁻¹	124
ZnS-V_S@Bi₂S₃@PVDF	Heterojunction	1 mol∙L⁻¹ Na₂S and Na₂SO₃	300 W Xe lamp, 100 W ultrasonic	H₂: 10.07 mmol∙g⁻¹∙h⁻¹	125
Ti₃C₂T_x@ZnO	Heterojunction	Triethanolamine solution	300 W Xe lamp, 200 W ultrasonic	H₂: ~16 μmol∙h⁻¹	121
H₂O₂ synthesis
Bi₄NbO₈Br nanosheets	Polarization modulation	Ethanol solution	300 W Xe lamp, 240 W ultrasonic	792 μmol∙g⁻¹∙h⁻¹	129
Nb-doped BaTiO₃@C	Polarization modulation	Ethanol solution	300 W Xe lamp, 150 W ultrasonic	1.36 mmol∙g⁻¹∙h⁻¹	130
BiFeO₃@BiOCl@BiVO₄	Heterojunction	Ethanol solution	50 W Xe lamp, 100 W ultrasonic	1.13 μmol∙L⁻¹∙min⁻¹	134
BiVO₄@BaTiO₃	Heterojunction	Ethanol solution	300 W Xe lamp, 150 W ultrasonic	4.68 μmol∙L⁻¹∙min⁻¹	135
ZnS@In₂S₃@BaTiO₃	Heterojunction	Ethanol solution	300 W Xe lamp, 150 W ultrasonic	3.78 μmol∙L⁻¹∙min⁻¹	136
LaFeO₃@ZnFe₂O₄@La₂O₃	Heterojunction	Pure water	300 W Xe lamp, 180 W ultrasonic	403 μmol∙g⁻¹∙h⁻¹	137
CN@PDI-CN	Homojunction	Pure water	300 W Xe lamp, 200 W ultrasonic	~10.43 μmol∙L⁻¹∙min⁻¹	138
V-BiOIO₃@FTCN	Heterojunction	Pure water	300 W Xe lamp, 200 W ultrasonic	~0.96 μmol∙L⁻¹∙min⁻¹	132
CO₂ reduction
ZnO nanorods	Morphology modulation	Pure water	300 W Xe lamp, ultrasonic	CO: 0.32 μL∙h⁻¹ CH₄: 0.03 μL∙h⁻¹	142
BiVO₄@PDMS-PZT	Heterojunction	Pure water	300 W Xe lamp, loading mass of ~9 g	CO: 1.37 μmol∙cm⁻²∙h^-1 CH₄: 2.41μmol∙cm⁻²∙h^-1	141
Organic synthesis
Ag@Bi₅O₇I	Surface engineering	CH₃OH solution, N₂	300 W Xe lamp, 60 W ultrasonic	NH₄⁺: 240.30 μmol∙L⁻¹∙g⁻¹∙min⁻¹	145
CuS@KTa_0.75Nb_0.25O₃	Heterojunction	CH₃OH solution, N₂	300 W Xe lamp, 60 W ultrasonic	NH₄⁺: 36.2 μmol∙L⁻¹∙g⁻¹∙min⁻¹	144
Bi₄NbO₈Br-V_O nanosheets	Surface engineering	Acetonitrile, benzylamine, O₂	300 W Xe lamp, ultrasonic	Conversion rate: 56.25% Selectivity: 90%	146
BaTiO₃@ZnIn₂S₄	Heterojunction	Acetonitrile, benzylamine, H₂O	300 W Xe lamp, ultrasonic	C-N coupling products: 5.59 mmol∙g⁻¹	147

Table 1

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Fig 7

Fig 8

Fig 9

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