轨道杂化在光催化与电催化中的研究进展

doi:10.1016/j.actphy.2025.100151

摘要/Abstract

摘要：

轨道杂化是调控光、电催化剂性能及能源器件转换效率的重要手段。本文系统综述了轨道杂化在光、电催化领域的研究进展、瓶颈及前景，涵盖其基本定义及典型分类。本文揭示了轨道杂化在调节材料成键效能、本征活性、选择性和稳定性方面的重要作用，综述了轨道杂化在光催化过程(包括光解水、光催化二氧化碳还原、光催化合成氨)和电催化过程(包括电催化析氢析氧、氧还原、二氧化碳还原等)的研究进展，并重点总结了轨道杂化的设计与调控策略(如合金化、元素掺杂、异质结构筑、缺陷工程、配位环境调控等)。最后，本文展望了基于轨道杂化调控催化剂性能所面临的关键挑战及发展前景。总之，轨道杂化为设计高活性、高选择性的光/电催化剂及构筑高效率、可持续的储能器件提供了新思路和新方向。

关键词: 轨道杂化, 光催化剂, 电催化剂, 能源器件, 调控策略

Abstract:

The conversion efficiency and stability of energy-related devices are significantly influenced by the photocatalysts and electrocatalysts. Orbital hybridization has emerged as a crucial strategy to enhance catalytic performance, with significant advancements made in recent years. This review focuses on the progress, challenges, and future prospects of orbital hybridization in photocatalysis and electrocatalysis. It begins with the fundamentals of orbital hybridization, covering basic principles and three typical classifications (reaction-level, structure-level, and cascaded orbital hybridization). It further introduces the vital roles of orbital hybridization in improving bonding efficiency, intrinsic activity, selectivity, and stability of the catalysts. Subsequently, recent advances in tuning orbital hybridization to enhance various photocatalytic and electrocatalytic reactions (e.g., HER, OER, ORR, and NRR) are highlighted. After that, modulation strategies (e.g., alloying, heteroatom doping, heterostructure construction, defect engineering, and coordination environment modulation) for orbital hybridization are summarized and discussed from both structural and reaction perspectives. Finally, this review presents the challenges faced in utilizing orbital hybridization to improve catalyst performance and outlines future prospects. By summarizing design strategies related to orbital hybridization, it offers new insights for the tailored construction and optimization of high-activity catalysts, advancing efficient and sustainable energy conversion and storage technologies.

Key words: Orbital hybridization, Photocatalysts, Electrocatalysts, Energy-related devices, Modulation strategies

吕宪伟, 丁信元, 龚家兴, 闫旭焕, 黄大勇, 耿建新, 袁忠勇. 轨道杂化在光催化与电催化中的研究进展[J]. 物理化学学报, 2026, 42(2), 100151. doi: 10.1016/j.actphy.2025.100151

Xian-Wei Lv, Xinyuan Ding, Jiaxing Gong, Xuhuan Yan, Dayong Huang, Jianxin Geng, Zhong-Yong Yuan. Research progress on orbital hybridization in photocatalysis and electrocatalysis[J]. Acta Phys. -Chim. Sin. 2026, 42(2), 100151. doi: 10.1016/j.actphy.2025.100151

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100151

https://www.whxb.pku.edu.cn/CN/Y2026/V42/I2/100151

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Classification	Catalyst^a	Hybrid type	Application	Performance	Ref.
Reaction-level orbital hybridization	SATi@CF/S	d−p	Li−S batteries	876 mAh g⁻¹ (0.5C)	[73]
	NG−InN₅	s−p	Na−S batteries	490.7 mAh g⁻¹ (2 A g⁻¹)	[74]
	Fe−N₃C₂−C	d−p	Li−S batteries	727.8 mAh g⁻¹ (6C)	[75]
Structure-level orbital hybridization	SnAg	d−p	NitRR	FE = 90.2% (E_{j =} 1.1 A cm⁻²)	[36]
	Ni−WO₂/CP	d−d	HER	83 mV (E_{j =} −10 mA cm⁻²)	[39]
	FePc/Eu₂O₃	f−d−p	ORR	0.931 V (E_1/2)	[43]
	Pt_4.31Ga NWs/C	d−p	ORR	0.92 V (E_1/2)	[58]
	V−Bi SAA	d−p	CO₂RR	FE = 90.5% (E = −0.5–−1.4 V)	[65]
	Nd/Co@NC	d−f	Zn-air batteries	1070.6 mW cm⁻²	[68]
	(MnFeCoNiZn)PS₃	d−p	OER	240 mV (E_j = 10 mA cm⁻²)	[76]
Cascaded orbital hybridization	Pd₃Pb	p−d and d−π*/σ	Li−O₂ batteries	7746 mAh g⁻¹	[21]

Modulation strategies	Catalyst ^a	Regulation effect	Application	Performance	Ref.
Alloying	Mo_0.25Nb_0.75Se₂/NG@PP	Tuning the d−band center	Li−S batteries	936 mAh g⁻¹ (6C)	[79]
	Pt₂₆Ir₇Fe₁₃Co₂₂Ni₃₂ NFs	Enhance 3d−5d orbital hybridization	Overall water splitting	1.594 V (E_j = 100 mA cm−2)	[80]
	CuPt/TiO₂	Enhance d−p and d−d orbital hybridization	Zn−NO₃ batteries	NH₃ yield = 2.34 mg h⁻¹ cm⁻² (10 mA cm⁻²)	[81]
Elemental doping	Co_0.75Fe_0.25P@C	Enhanced d−p orbital hybridization	Li−S batteries	726.3 mAh g⁻¹ (6C)	[34]
	Pd₃Sn MAs	Tuning the d−band center of Pd	EGOR	1.69 A mg_Pd⁻¹	[35]
	Cu₃P@NPPC	Regulating the electronic structure of Cu	ORR	0.78 V (E_1/2)	[87]
Heterojunction interface	Fe₃O₄/CeO₂@N−CNFs	Tuning the d−band center	Zn-air batteries	794.2 mAh g⁻¹ (5 mA cm⁻²)	[101]
	Pd−PdSe HNSs	Enhanced d−p orbital hybridization	EGOR	FE_C1 = 38.9% (E = 0.9 V)	[102]
	NiMo@NiFeCe-LDH	Tuning the d−band center	OER	215 mV (E_j =10 mA cm−2)	[103]
Defect engineering	Ru@PRC	Regulating the electronic structure of Ru	HER	28 mV (E_j =10 mA cm−2)	[116]
	Fe_H−N−C	Enhanced d−p orbital hybridization	ORR	0.91 V (E_1/2)	[118]
	V−Bi NS	Facilitating the electronic delocalization of Bi	CO₂RR	FE_formate = 96.2% (E_j = −300 mA cm−2)	[110]
Coordination microenvironment	Mn−N₂/CNs@S	Enhanced d−p orbital hybridization	Na−S batteries	458 mAh g⁻¹ (3C)	[130]
	Alk−MXene/FePc	Promoting orbital splitting and regulating spin state	ORR	0.924 V (E_1/2)	[135]
	Fe₅−Cu−N−mC	Enhanced hybridization between Fe d_z2 and O p_z orbital	ORR	0.92 V (E_1/2)	[137]

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