Innovative strategies in noble and earth abundant metal single-atom-based photocatalysts for hydrogen production

doi:10.1016/S1872-2067(26)65191-1

Chinese Journal of Catalysis ›› 2026, Vol. 90: 1-26.DOI: 10.1016/S1872-2067(26)65191-1

Innovative strategies in noble and earth abundant metal single-atom-based photocatalysts for hydrogen production

Ikram Ullah^a, Risheng Duan^a, Muhammad Amin^b, Waqar Ahmad Qureshi^a, An-Wu Xu^c^,^*(), Pei Zhao^a^,^*(), Ning Qin^a^,^*()

^a School of Energy and Power Engineering, Shandong University, Jinan 250061, Shandong, China
^b Department of Chemical, Petroleum & Petrochemical Technology, Mir Chakar Khan Rind University of Technology, Dera Ghazi Khan 32200, Pakistan
^c Division of Nanomaterials and Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2026-01-01 Accepted:2026-03-09 Online:2026-11-05 Published:2026-09-09
About author:An-Wu Xu (Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China) is a Professor at the University of Science and Technology of China. He received his Ph.D. degree in Applied Chemistry from the same University in 1998. He has published more than 270 SCI papers in prestigious journals, including J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater., ACS Nano, ACS Energy Lett., ACS Catal., and Adv. Funct. Mater.
Pei Zhao (School of Energy and Power Engineering, Shandong University) is a Professor at Shandong University. She received her Ph.D. degree from the Functional Ceramic Materials Group at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences. From 2014 to 2015, she was a Postdoctoral Fellow at the Max Planck Institute for Plasma Physics, Germany. From 2015 to 2022, she held positions as a Postdoctoral Fellow, Research Associate, and Research Assistant Professor at the University of Waterloo, Canada. Her research interests mainly focus on photocatalysis, water splitting, environmental monitoring, microfluidic technology and device development, and the design and preparation of materials for water pollution treatment.
Ning Qin (School of Energy and Power Engineering, Shandong University) as a Professor at Shandong University. He received his Ph.D. degree in Mechanical Engineering at the University of Waterloo, Canada, in 2017. From 2018 to 2019, he was a Postdoctoral Fellow at Harvard Medical School, United States. From 2019 to 2022, he served as a Research Associate and Postdoctoral Fellow at the University of Waterloo, Canada. His research interests mainly focus on nano and microscale fluid dynamics, carbon capture, storage and utilization, and microengineering for advanced diagnostics and therapeutics.
Supported by:
China/Shandong University International Postdoctoral Exchange Program, the Shandong Provincial Natural Science Foundation(ZR2024ME103);China/Shandong University International Postdoctoral Exchange Program, the Shandong Provincial Natural Science Foundation(ZR2023QE305);Shandong Excellent Young Scientists Fund Program (Overseas)(2023HWYQ-021);National Natural Science Foundation of China(52306100);National Natural Science Foundation of China(22271266);USTC-Yanchang Petroleum New Energy Joint Research Project(2022ZKD-02);Fundamental Research Funds for the Central Universities(YD23440002001)

Abstract

Abstract:

This review presents a comprehensive overview of noble (Pt, Pd, Ag, Au, Ru, and Rh) and earth abundant metals (Co, Cu, Ni, Fe, and Mo) single-atom-based photocatalysts (SACs) for hydrogen (H₂) production. We first highlight the fundamental of SACs followed by rational design strategies to achieve atomic-level distribution, and increase the density of active sites. Then, thoroughly summarize the enhanced H₂ production activity of noble and earth abundant metal-based SACs. Moreover, insights into the charge transfer mechanisms, such as charge separation, transfer, and spatially defined electron delocalization to unravel the structure-activity relationship and coordination-dependent catalytic performance. Finally, we discuss recent challenges and prospects for designing highly effective SACs. Overall, this review provides a valuable guidance by highlighting fundamental principles of SACs, performance assessment, and mechanistic insights toward practical solar-to-H₂ conversion.

Key words: Noble metals, Earth abundant metals, Single-atom-based photocatalysts, Coordination environment, H₂ production, Mechanism

Ikram Ullah, Risheng Duan, Muhammad Amin, Waqar Ahmad Qureshi, An-Wu Xu, Pei Zhao, Ning Qin. Innovative strategies in noble and earth abundant metal single-atom-based photocatalysts for hydrogen production[J]. Chinese Journal of Catalysis, 2026, 90: 1-26.

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Figures/Tables 16

Fig. 1. Schematic diagram presenting the key aspects covered in this review.

Fig. 2. Typical photocatalytic H2 evolution mechanism on semiconductors (a), semiconductors with nanoparticle cocatalysts (b), semiconductor with SA as cocatalysts (c), and semiconductors with SA as trap sites (d).

Fig. 3. (a) Preparation mechanism of Pt/FAPbBr3-xIx. (b) XANES spectra at the Pt L3-edge for Pt foil, H2PtCl6, and 1.8-Pt/FAPbBr3-xIx. k3-weighted FT spectra of the EXAFS data (c), R-space data analysis and fitting (d) for 1.8-Pt/FAPbBr3-xIx compared with two reference samples. (e) Simulated model for the configuration of Pt/FAPbBr3-xIx. (f) H2 production rates of different photocatalysts. (g) Stability plots of 1.8-Pt/FAPbBr3-xIx over 10 cycles. (h) Free energy patterns for H* adsorption on Pt, FAPbBr3-xIx, and Pt/FAPbBr3-xIx with the inset illustrating the related mechanism. (i) Schematic diagram of the photocatalytic mechanism in Pt/FAPbBr3-xIx. Adopted with permission from Ref. [49]. Copyright 2022, Royal Society of Chemistry.

Table 1 Photocatalytic H2 production over representative Pt SACs.

Photocatalyst	Light source	Sacrificial agent	H₂ production (mmol h⁻¹ g⁻¹)	AQE (%)	Ref.
ZOS-SAPt	300 W Xe lamp (AM 1.5 filter)	Na₂S/Na₂SO₃	9.66	8.28 at 365 nm	[57]
0.72wt% Pt₁@TpPa-1	300 W Xe lamp (λ ≥ 420 nm)	sodium ascorbate	0.719	0.38 at 420 nm	[58]
Pt SA-P25	LED (365 nm)	—	4.60	—	[59]
Pt-SAs@Pd-PCN-222-NH₂	300 W Xe lamp (λ ≥ 420 nm)	triisopropanolamine	16.591	—	[60]
TiO₂-BNS-Pt_0.05	150 W Xe lamp (AM 1.5G)	methanol	0.688	8.48 at 325 nm	[61]
Cd-Pt₂-SSs	150 W Xe lamp (UV-Visible)	Na₂S/Na₂SO₃	154.68	≈91.1 at 365 nm	[62]
TCOF/Pt SA	300 W Xe lamp	benzylamine	0.5018	—	[63]
PtSAs-Au_2.5/PCN	300 Xe lamp (λ ≥ 420 nm)	TEOA	13.70	—	[64]
Sb₂S₃-Pt_0.9%	300 W Xe lamp (simulated)	TEOA	1.37	5.41 at 700 nm	[65]
V_N2c-UCN-Pt	300 W Xe lamp (λ ≥ 395 nm)	TEOA	1.774	2.43 at 380 nm	[66]
PFC-1@Pt	300 W Xe lamp (λ > 420 nm)	ascorbic acid	2.2025	—	[67]
Pt_SA/TiO₂(Pr)	UV	methanol	196.43	42.07 at 365 nm	[68]
Pt SAs/g-C₃N_5-_x-O	300 W Xe lamp (λ > 420 nm)	TEOA	1.8092	—	[69]
Pt SA-NS	LED (365 nm)	methanol	11.7	—	[70]
0.63%Pt₁-N-CN₁	300 W Xe lamp (λ > 320 nm)	TEOA	30	21.3 at 400 nm	[71]
Au@Pt-SA/CdS Y-S	300 W Xe lamp (λ > 420 nm)	Na₂S/Na₂SO₃	10.9	—	[72]
1.42wt% Pt₁/TiO₂	300 W Xe lamp (200-2500 nm)	methanol	95.180	—	[73]
Pt_0.08SAC₃N_4.6	250 W mercury vapor lamp (Vis-light)	TEOA	64.1	25.3 at 420 nm	[74]
TAPAT-TFP-Pt₁-0.31 wt%	300 W Xe lamp (λ ≥ 420 nm)	ascorbic acid	2.39	0.24 at 500 nm	[75]
Pt₁/CS_v	300 W Xe lamp (λ > 420 nm)	TEOA	0.8272	17.6 at 420 nm	[76]

Fig. 4. (a) Diagram of the synthesis process for Pd-InNb-10. Normalized Pd K-edge XANES spectra (b) and k2-weighted Pd K-edge FT-EXAFS spectra (c) in R-space for 1.0 wt%Pd-InNb-10 with reference Pd foil and PdO samples. (d) H2 evolution rate of 1.0 wt%Pd-InNb-10 with varying Pd amounts under simulated solar light illumination. (e) Wavelength-dependent AQE of H2 production. (f) Recycling tests for the optimal sample. (g) Mechanism diagram of the optimal composite upon simulated sunlight driven photocatalytic H2 production. Adopted with permission from Ref. [89]. Copyright 2025, Elsevier.

Table 2 Representative Pd SACs for photocatalytic H2 evolution.

Photocatalyst	Light source	Sacrificial agent	H₂ production (mmol h⁻¹ g⁻¹)	AQE (%)	Ref.
3.5% MAC-1/g-C₃N₄	300 W Xe lamp (λ > 420 nm)	TEOA	22.3	1.61 at 405 nm	[90]
Pd_0.03/ZIS	300 W Xe lamp (AM 1.5 G)	—	1.0379	4.79 at 380 nm	[91]
Pd-TiO₂	300 W Xe lamp	methanol	24.59	23.4 at 365 nm	[92]
Pd_1+NPs/CCN₃	300 W Xe lamp (λ > 320 nm)	TEOA	24.1	17.1 at 400 nm	[93]
Pd-MOF	LED (450 nm)	ascorbic acid	21.3	—	[94]
Pd/Cd_0.1Zn_0.9S	300 W Xe lamp (λ > 420 nm)	—	0.6082	—	[95]
0.10Pd_SA-CuCo₂S₄	250 W mercury vapor lamp	Na₂S/Na₂SO₃	39.559	15.57 at 420 nm	[96]
0.3Pd SA/CdS-H	300 W Xe lamp (λ > 420 nm)	lactic acid	22.23	16 at 380 nm	[97]

Fig. 5. (a) Normalized N K-edge XANES spectra of Ag1-CN and 50-Ag1+NPs-CN. Ag K-edge XANES spectra (b), FT-EXAFS spectra (c), and WT of the Ag K-edge EXAFS spectra (d) for Ag foil, Ag2O, and the optimal sample. (e) H2 evolution rates of samples. Recycling tests (f) and mechanism (g) of 50-Ag1+NPs-CN upon solar light illumination. Adopted with permission from Ref. [105]. Copyright 2025, John Wiley and Sons.

Fig. 6. (a) Schematic of in-situ preparation of Au SAs on PAF-164 by pre-metallated building blocks. Au L3-edge XANES spectra (b) and FT-EXAFS spectra (c) of Au foil, Au2O3, HAuCl4, Au5%-SAs PAF-164, and Au100%-SAs-PAF-164. (d,e) EXAFS fitting plots of Au5%-SAs PAF-164 and Au100%-SAs-PAF-164. (f) H2 production over synthesized photocatalysts. (g) Five-cycle stability test of Au100%-SAs-PAF-164. (h) Charge transfer process in PAF-164 and Aux-SAs-PAF-164 for H2 evolution upon visible-light illumination. Adopted with permission from Ref. [111]. Copyright 2024, John Wiley and Sons.

Fig. 7. (a) Scheme for the preparation of photocatalysts. Ru K-edge XANES (b), FT-EXAFS spectra in R-space (c), and WT EXAFS spectra (d) of Ru1/CRP compared with Ru foil and RuO2. (e) Schematic representation of the proposed charge dynamics in CRP, Ru1/CRP, and Ru1-NP/CRP and Ru1+RuNP/CRP. Adopted with permission from Ref. [123]. Copyright 2024, John Wiley and Sons. (f) H2 production rate before and after loading Ru atoms. (g) Schematic illustration of the mechanism of H2 evolution over COF-Cu3TG. Adopted with permission from Ref. [131]. Copyright, 2024, John Wiley and Sons.

Fig. 8. (a) Synthesis process of Rh1@MoS2/CZS-SVs photocatalyst. (b-d) HAADF-STEM images of Rh1@MoS2/CZS-SVs, where red circles represent atomically dispersed Rh SAs. (e) H2 evolution rates of different samples. (f) Charge transfer mechanism for Rh1@MoS2/CZS-SVs. Adopted with permission from Ref. [132]. Copyright 2025, Elsevier.

Fig. 9. (a) Illustration of the synthesis of Co-RuOx/TiO2. Co K-edge XANES spectra (b), FT spectra in R-space (c) for Co-RuOx/TiO2 and reference samples. (d) EXAFS fitting plot in R-space for Co-RuOx/TiO2. (e) H2 evolution rates as a function of photocatalyst concentration. (f) H2 production rates in seawater at 1.75 g L−1 for various photocatalysts. Adopted with permission from Ref. [138]. Copyright 2023, John Wiley and Sons. (g) Photocatalytic H2 production mechanism over Co1-PCTF. Adopted with permission from Ref. [149]. Copyright 2024, Royal Society of Chemistry.

Table 3 outlines latest Co SACs for H2 production.

Photocatalyst	Light Source	Sacrificial agent	H₂ production (mmol h⁻¹ g⁻¹)	AQE (%)	Ref.
Co-N-C/g-C₃N₄	12 W LED-lamp (λ = 420 ± 10 nm)	TEOA	1.180	—	[152]
30%Co@PCMP	300 W Xe-lamp (λ > 420 nm)	TEOA	1.72	2.05 at 420 nm	[153]
Co/P/CN-sc	300 W Xe-lamp (λ > 420 nm)	TEOA	3.7304	—	[154]
Co-CCN-PTI	300 W Xe-lamp (λ > 420 nm)	TEOA	3.538	20.88 at 425 nm	[155]
Co_0.10-SA/CTF	300 W Xe-lamp (λ = 420 nm)	TEOA	1.29318	1.72 at 420 nm	[156]
1.5%Co/PCN	300 W Xe-lamp (λ = 400 nm)	TEOA	0.8925	—	[157]
Co(N, S)/C₃N₄	10 W LED-lamp (λ = 420 nm)	ethanol	9.99	15.82 at 420 nm	[158]
CNA/10Co-dcbpy	300 W Xe-lamp (λ > 400 nm)	TEOA	1.016	3.43 at 420 nm	[159]

Fig. 10. (a) Schematic representation of Cu SAs on TiO2 via surface doping approach. Adopted with permission from Ref. [166]. Copyright 2023, Elsevier. Normalized Cu K-edge XANES spectra (b) and Cu K-edge K2-weighted FT EXAFS spectra (c) of samples. (d) Illustration of CuSA-OV-Ti3c HAAS construction, displaying CuSA replacement at Ti5c sites next to Ti3c based EXAFS analysis. (e) H2 evolution over HAASC catalysts with various Cu amounts. (f) H2 evolution rates over FT111 and CuSA(0.9)FT111. (g) Photocatalytic H2 production stability test of CuSA(0.9)FT111. (h) Gibbs free energy plot for H2 evolution reaction at CuSA-OV-Ti3c (green) and Ti5c-O-Ti3c (black) sites. (i) Proposed H2O activation path and free energy pattern of intermediates for CuSA-OV-Ti3c HAAS (green) and Ti5c-O-Ti3c AAS (black). (j) Proposed photocatalytic water splitting reaction mechanism over CuSA-OV-Ti3c HAASC (grey, brown, red, and pink color indicate Ti, Cu, O, and H atoms, respectively). Adopted with permission from Ref. [168]. Copyright 2024, John Wiley and Sons.

Fig. 11. (a) Schematic illustration for the synthesis of 0.74%NiN2S/SA-CN. Adopted with permission from Ref. [185]. Copyright 2022, John Wiley and Sons. Intensity profiles for site A (b) and site B (c). (d) FT-EXAFS spectra of Ni foil, NiO, CuCNi1/TiO2, and Ni1/TiO2. (e) FT-EXAFS fitting plots of Ni1/TiO2 and CuCNi1/TiO2 in k space. Photocatalytic H2 production stability test (f) and AQE (g) for CuCNi1/TiO2 upon 350 nm. (h) Photocatalytic H2 production mechanism over CuCNi1/TiO2. Adopted with permission from Ref. [187]. Copyright 2024, John Wiley and Sons.

Fig. 12. (a) Schematic representation for synthesis of FeN4-CN and FeN3P2-CN. Fe K-edge XANES spectra (b) and FT K-edge EXAFS spectra (c) of FeN3N2-CN, FeN4-CN, and Fe foil. (d) R space fitting curves of FeN3P2-CN and FeN4-CN. (e) Average H2 evolution rates for various photocatalysts upon visible-light illumination. (f) Quantum efficiency of H2 production for FeN3P2-CN. (g) Cycling durability test of H2 production over FeN3P2-CN. Adopted with permission from Ref. [189]. Copyright 2024, John Wiley and Sons.

Fig. 13. (a) Schematic illustration of Mo1@CNNTs synthesis. Mo K-edge XANES (b) and K-edge FT-EXAFS (c) spectra of Mo1@CNNTs and reference samples. (d) EXAFS fitting curves in R space with inset in k space. EXAFS WT of Mo1@CNNTs (e), Mo foil (f), and MoO3 (g). (h) Time-dependent H2 production activity over different samples. (i) H2 production rates over various samples. (j) Cycling stability tests of Mo1@CNNT. (k) Possible charge transfer mechanism of H2 production. Adopted with permission from Ref. [201]. Copyright 2025, Elsevier.

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Innovative strategies in noble and earth abundant metal single-atom-based photocatalysts for hydrogen production

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