Progress on facet engineering of catalysts for application in photo/electro-catalysis

doi:10.1016/S1872-2067(23)64600-5

Abstract

Abstract:

The conversion and storage of solar or electrical energy into chemical energy through photo/electro-catalysis technology shows fascinating potential for alleviating the energy crisis. The application of facet engineering in photo/electrocatalytic materials has shown significant advantages, making it an attractive and challenging topic at the intersection of physics and chemistry. In recent years, from basic scientific research to practical applications, facet engineering has made significant progress in photo/electro-catalytic reactions. In this review, we mainly focus on the microscopic mechanisms of facet engineering and how it specifically affects photo/electro-catalytic reactions, including CO₂ reduction, hydrogen evolution, and nitrogen reduction. The microscopic mechanisms are elucidated and direct evidence for improving catalytic reactions is revealed through advanced spectroscopic characterization and theoretical analysis. Based on the microscopic mechanisms of facet engineering, the design principles and breakthrough directions for facet engineering are proposed, such as LSPR and single atom modification etc. In particular, we emphasize the controllable preparation methods for facet exposure from the aspects of capping agents, pH regulation and precursor hydrolysis, etc. Finally, the outlooks and future development prospects of facet engineering are briefly discussed.

Key words: Facet engineering, Photo/electro-catalysis, Microscopic mechanism, Controllable preparation, Design principle

Qi Li, Jiehao Li, Huimin Bai, Fatang Li. Progress on facet engineering of catalysts for application in photo/electro-catalysis[J]. Chinese Journal of Catalysis, 2024, 58: 86-104.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64600-5

https://www.cjcatal.com/EN/Y2024/V58/I3/86

Figures/Tables 23

Fig. 1. The schematic introduction to the content of this review.

Fig. 2. (a) The CVs and in-situ STM images of Pt {111}. Reprinted with permission from Ref. [17]. Copyright 2017, American Chemical Society. (b) Pt nanocrystals enclosed by different facets. Reprinted with permission from Ref. [18]. Copyright 2011, Royal Society of Chemistry. (c) In-situ XAS of the Cu K-edge. Reprinted with permission from Ref. [19]. Copyright 2019, American Chemical Society.

Fig. 3. (a) The different behaviors of water adsorption on {101} and {001} facets. Reprinted with permission from Ref. [26]. Copyright 2016, American Chemical Society. (b) The Gibbs-free energy of CO2RR and CO2 adsorption behavior (insert) on {101} and {001} facets. Reprinted with permission from Ref. [28]. Copyright 2020, American Chemical Society.

Fig. 4. (a) The band alignments of {001}/{110} and {010}/{102} facet junctions. Reprinted with permission from Ref. [33]. Copyright 2022, Elsevier. (b) The band alignment at the interface of the {101} and {001} facet. Reprinted with permission from Ref. [34]. Copyright 2018, Wiley. (c) The KPFM and (d) surface potential images of facet-defined BiVO4. Reprinted with permission from Ref. [35]. Copyright 2020, Wiley. (e,f) The Z-Scheme mechanism of facet heterojunction.

Fig. 5. (a) The spatial charge transfer in Bi2MoO6. Reprinted with permission from Ref. [40]. Copyright 2017, Wiley. (b) The PDOS diagrams of BiOCl {001} and {110} facets. Reprinted with permission from Ref. [42]. Copyright 2015, Wiley. (c) The DOS diagrams of CeO2 {100} and {111} facet. Reprinted with permission from Ref. [43]. Copyright 2015, American Chemical Society. (d) The schematic diagram of different holes average diffusion distance in different facets. Reprinted with permission from Ref. [45]. Copyright 2017, Wiley.

Fig. 7. TiO2 with different facets exposed.

Table 1 The effect of the capping agents on facet.

Catalyst	Capping agents	Facet	Ref.
TiO₂	HF	{001}	[54]
TiO₂	NH₄F	{001}	[55]
TiO₂	TiCl₄	{100}	[57]
TiO₂	NaF+TiCl₄	{001}/{101}	[56]
TiO₂	TiF+TiCl₄	{001}/{101}	[57]
TiO₂	[bmim][BF₄]	{001}/{101}	[58]
CaCu₃Ti₄O₁₂	KCl	{001}/{111}	[59]
CaSnO₃	NaCl/KCl	{100}/{100}/{111}	[60]
NH₂-MIL-125	tannic acid	{100}	[61]

Fig. 8. (a) The free energy and reaction energy barriers for CO2 reduction to formic acid on Pd with different facets exposed. Reprinted with permission from Ref. [72]. Copyright 2016, American Chemical Society. (b) The CO2 reduction procedure. Reprinted with permission from Ref. [83]. Copyright 2021, Wiley. (c) The atomic diffusion structure and local density of states on Cu-based material. Reprinted with permission from Ref. [76]. Copyright 2020, American Chemical Society.

Table 2 The selectivity of Cu-based materials with different facet exposures.

Cu-based materials	Facet	Selectivity	Faradaic efficiency (%)	Ref.
Cu nanocube	{100}/{211}	C₂₊	60	[79]
Cu thin film	{100}	C₂₊	86.5	[80]
AuCu	{111}	C₂H₄	41.5	[81]
Cu₂O	{100}	C₂₊	67.5	[74]
Cu₂O	{111}/{100}	C₂H₄	59	[77]
S-Cu₂O	{100}	HCOOH	80	[82]
Cu(OH)₂	{100}/{110}	C₂₊	87	[83]
Cu₂CO₃(OH)₂	{111}/{200}/{220}	C₂H₄	67.2	[84]

Fig. 10. (a) The migration pathway of charges driven by internal electric fields. Reprinted with permission from Ref. [87]. Copyright 2022, Nature. (b) The mechanism of van der Waals gaps (VDWGs) induced defect. Reprinted with permission from Ref. [88]. Copyright 2021, Nature. (c) The carrier migration behavior on the different facets of BiVO4. Reprinted with permission from Ref. [89]. Copyright 2018, Wiley.

Fig. 11. The photocatalytic CO2 reduction reaction pathway on Cu2O.

Fig. 12. (a) The PDOS of Pt atoms on different facets. Reprinted with permission from Ref. [96]. Copyright 2022, Elsevier. (b) The free energy diagram of Ni and Ni3N for HER. Reprinted with permission from Ref. [99]. Copyright 2022, Wiley. (c) The free energy diagram of CoP {011} for HER. Reprinted with permission from Ref. [100]. Copyright 2018, Wiley. (d) The HER performance of FeS2 at pH 13. Reprinted with permission from Ref. [102]. Copyright 2017, American Chemical Society.

Fig. 13. The mechanism of photocatalytic water splitting to hydrogen.

Fig. 15. (a) The facet dependent energy band potential of Cu2O. Reprinted with permission from Ref. [106]. Copyright 2022, American Chemical Society. (b) The modification of RuO2 cocatalysts on WO3. Reprinted with permission from Ref. [108]. Copyright 2022, Wiley. (c) The charge transfer mechanism between Ta3N5 photocatalysts and CoOx cocatalyst. Reprinted with permission from Ref. [109]. Copyright 2016, American Chemical Society.

Fig. 16. The mechanism of electrocatalytic reduction of nitrogen to ammonia.

Fig. 17. (a) The free energy of Pd {100}, Pd {111}, and Pd {110} for NRR. Reprinted with permission from Ref. [112]. Copyright 2020, Wiley. (b) The Faraday efficiency of ammonia production in Pt alloy. Reprinted with permission from Ref. [113]. Copyright 2021, Royal Society of Chemistry. (c) The PDOS of d-bands for Pt-5d and Fe-3d sites on {311} facet. Reprinted with permission from Ref. [115]. Copyright 2021, Science Citation Index Expanded. (d) The free energy diagram of Mo2C{200} for NRR. Reprinted with permission from Ref. [117]. Copyright 2020, American Chemical Society.

Table 3 The yields and selectivity of NRR for different materials.

Catalyst	Electr- olyte	Potential (RHE/V)	Yield (μg mg^‒1_cath^‒1)	Faradaic efficiency (%)	Ref.
Pd{100}	Li₂SO₄	0	24.3	36.6	[112]
Pt{410}-La	HCl	‒0.2	71.4	35.6	[113]
Pt{710}-Ir	HCl	‒0.3	28	40.8	[114]
Pt{311}-Fe	KOH	‒0.05	18.3	7.3	[115]
LiFeO₂{111}	NaOH	‒0.5	40.5	16.4	[116]
Mo₂C{200}	Na₂SO₄	‒0.55	—	40.2	[117]
Ni₃S₄{110}/{100}	K₂SO₄	‒0.2	1.28	6.8	[118]

Fig. 20. The modification strategies of facet engineering.

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