Towards highly efficient selective hydrogenation: The role of single-atom catalysts

doi:10.1016/S1872-2067(25)64906-0

Chinese Journal of Catalysis ›› 2026, Vol. 81: 69-96.DOI: 10.1016/S1872-2067(25)64906-0

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Towards highly efficient selective hydrogenation: The role of single-atom catalysts

Peikun Li^a, Jinghui Lyu^a(), Yiyong Zhao^a, Han Wu^a, Xianghao Zhang^a, Qiannan Lu^a, Yizhi Xiang^b, Blaž Likozar^c, Matej Huš^c^,^d, Adriana Zaleska-Medynska^e, Xiaonian Li^a()

^a College of Chemical Engineering, State Key Laboratory of Green Chemical Synthesis and Conversion, Zhejiang Key Laboratory of Surface and Interface Science and Engineering for Catalysts, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China
^b Department of Chemical and Biomedical Engineering, University of Missouri, Columbia, MO 65211, USA
^c National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering, SI-1000 Ljubljana, Slovenia
^d Association for Technical Culture of Slovenia (ZOTKS), SI-1000 Ljubljana, Slovenia
^e Department of Environmental Technology, Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, Gdansk 80-308, Poland

Received:2025-07-15 Accepted:2025-09-28 Online:2026-02-18 Published:2025-12-26
Contact: *E-mail: lyujh@zjut.edu.cn (J. Lyu),xnli@zjut.edu.cn (X. Li).
About author:Peikun Li (College of Chemical Engineering, Zhejiang University of Technology (ZJUT)) is currently pursuing his Master’s degree under the supervision of Professor Jinghui Lyu. His research is broadly centered on industrial catalysis, with an emphasis on the rational design and synthesis of advanced catalytic materials, catalytic reaction engineering, and the development of transition metal-based catalytic systems. He has a particular interest in zeolite, single-atom catalysts, and electrocatalytic processes, where he seeks to unravel structure-activity relationships and establish strategies for improving catalytic efficiency, selectivity, and long-term stability.
Jinghui Lyu (College of Chemical Engineering, Zhejiang University of Technology (ZJUT)) received his B.S. in 2006 and Ph.D degree in 2014 from ZJUT under the supervision of Prof. Xiaonian Li. He worked as a technology and engineering researcher (2006-2008) and as a postdoctoral fellow (2014-2016), contributing to the industrialization of several lab-scale catalytic technologies. From 2019 to 2020, he was a visiting scholar at Western University, Canada. His research focuses on heterogeneous catalysis, particularly the design and application of porous materials and supported metal catalysts for green chemical processes, including selective hydrogenation, oxidation reactions, and continuous flow catalysis. He received First Prize of the National Ministry of Education Technological Invention Award for green catalytic hydrogenation processes, Second Prize of Zhejiang Provincial Science and Technology Progress Award and the Second Prize of the China Chemical Society Science and Technology Progress Award for contributions to the continuous and miniaturized chemical processes. The green hydrogenation process and catalyst, along with the related research on continuous and miniaturized chemical processes have already been industrialized. He has led multiple national research projects in China and successfully transferred patented catalytic technologies to industrial practice.
Xiaonian Li (College of Chemical Engineering, Zhejiang University of Technology (ZJUT)), PhD, Professor, is a doctoral supervisor at ZJUT, a Fellow of the Canadian Academy of Engineering, and former President of the university. He received his PhD from the Chinese Academy of Sciences in 1998 and conducted postdoctoral research at the University of British Columbia and Oak Ridge National Laboratory. His research focuses on industrial catalysis and green chemical processes. He has received the National Technological Invention Second Prize and holds several academic roles, including member of the State Council Academic Evaluation Committee and executive director of the Chemical Industry and Engineering Society of China.
Supported by:
National Natural Science Foundation of China(NSFC22278368);National Natural Science Foundation of China(NSFC22578399);Zhejiang Provincial Natural Science Foundation(LY21B060006);Technology Transfer Project between Zhejiang University of Technology and Industry(KYY-ZH-20240069);Energy Revolution S &T Program of Yulin Innovation Institute of Clean Energy(E412022701)

Abstract

Abstract:

Selective hydrogenation is crucial in various chemical processes and environmental applications, where precise control of reactivity and selectivity is essential for the efficient production of high-purity products. Single-atom catalysts (SACs), with atomically dispersed metal sites, could bridge homogeneous and heterogeneous catalysis and have emerged as a transformative platform for highly efficient selective hydrogenation with minimal use of critical raw materials as catalysts. This review explores the latest advancements in this cutting-edge area. Specifically, we analyze the structure-activity relationships, such as catalytic properties and mechanisms that determine the reactivity and selectivity of such catalytic systems. Furthermore, we discuss challenges, including stability, synthesis scalability, coordination environment tuning, atomistic modeling, and mechanistic insights, while identifying research opportunities for optimizing SACs performance. If these challenges are addressed, SACs hold the potential to revolutionize selective hydrogenation processes, offering sustainable and highly efficient catalytic solutions for industrial applications.

Key words: Single atom catalysis, Selective hydrogenation, H₂ activation, Catalyst design, Atomistic modeling

Peikun Li, Jinghui Lyu, Yiyong Zhao, Han Wu, Xianghao Zhang, Qiannan Lu, Yizhi Xiang, Blaž Likozar, Matej Huš, Adriana Zaleska-Medynska, Xiaonian Li. Towards highly efficient selective hydrogenation: The role of single-atom catalysts[J]. Chinese Journal of Catalysis, 2026, 81: 69-96.

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Figures/Tables 24

Fig. 1. Applications of SACs in hydrogenation.

Fig. 2. Development of SACs for hydrogenation from 2011 to 2025 [26,39-61]. Reprinted with permission from Ref. [26]. Copyright 2011, Springer nature. Reprinted with permission from Ref. [39]. Copyright 2003, John Wiley and Sons. Reprinted with permission from Ref. [40]. Copyright 2013, John Wiley and Sons. Reprinted with permission from Ref. [41]. Copyright 2014, Springer nature. Reprinted with permission from Ref. [42]. Copyright 2015, American Chemical Society. Reprinted with permission from Ref. [43]. Copyright 2016, John Wiley and Sons. Reprinted with permission from Ref. [44]. Copyright 2017, American Chemical Society. Reprinted with permission from Ref. [46]. Copyright 2018, Springer nature. Reprinted with permission from Ref. [48]. Copyright 2019, American Chemical Society. Reprinted with permission from Ref. [51]. Copyright 2020, Springer nature. Reprinted with permission from Ref. [52]. Copyright 2021, American Chemical Society. Reprinted with permission from Ref. [53]. Copyright 2021, Springer nature. Reprinted with permission from Ref. [54]. Copyright 2023, John Wiley and Sons. Reprinted with permission from Ref. [55]. Copyright 2024, Springer nature. Reprinted with permission from Ref. [56]. Copyright 2025, American Chemical Society. Reprinted with permission from Ref. [57]. Copyright 2020, Elsevier. Reprinted with permission from Ref. [58]. Copyright 2021, Springer nature. Reprinted with permission from Ref. [59]. Copyright 2022, American Chemical Society. Reprinted with permission from Ref. [60]. Copyright 2023, Springer nature. Reprinted with permission from Ref. [61]. Copyright 2024, John Wiley and Sons.

Table 1 Summary of advantages and disadvantages of preparation methods for SACs.

Preparation method	Advantage	Disadvantag
Wetness impregnation	simple to operate	metal atoms generally do not achieve uniform dispersion on the surface of the support
Ion exchange	enables the synthesis of highly loaded single atoms on the support surface	only applicable for the synthesis of limited types of SACs
Co-precipitation	suitable for the preparation of composite oxides with two or more uniformly dispersed metal elements	1. preparation parameters exert a significant influence on catalyst performance 2. a portion of active atoms remain unexposed and thus cannot participate in catalytic reactions
Templated hydrothermal	simple and easy to operate	same as ion exchange
Metal leaching	preparation of monodispersed catalysts by a two-step method	1. only suitable for a limited range of specific metals and support materials 2. the preparation process is associated with environmental pollution
Facile adsorption	simple and easy to operate	a proper interaction between the active metal components and the catalyst support is required
Strong electrostatic adsorption	suitable for the preparation of high-quality precious metal SACs	the adsorption behavior is influenced by multiple factors
Pyrolysis synthesis	facilitates straightforward preparation of SACs	demands a high pyrolysis temperature
Ball-milling	simple, scalable production, green	the catalysts are prone to agglomeration
Two-step doping	high stability	1. it is necessary to provide mobile atoms and a support capable of capturing mobile species 2. high-temperature synthesis necessitates a high-energy atom/ion generator
Host-guest strategy	1. strong stabilization of isolated atoms 2. tunable coordination environment	1. limited to supports with suitable porosity 2. complex synthesis routes
Photoreduction	the approach requires no specialized equipment and is straightforward to implement	the catalytic active centers are generally non-uniform
Atomic layer deposition	1. precise manipulation of process parameters 2. superior deposition uniformity and high reproducibility 3. the loading of singly dispersed atoms can be tailored by adjusting the number of deposition cycles	1. only support materials functionalized with appropriate ligands or functional groups are viable for selection 2. not amenable to large-scale commercial manufacturing
Atom trapping	the operation process is simple	same as two-step doping
One-pot wet chemistry	1. no specialized experimental setup or multi-step reaction conditions are required, which is conducive to large-scale production 2. high loading of isolated metal atoms can be achieved	limited by the solubility of different precursors
Cyclic voltammetry	less additives are demanded and no interfering products are generated	an electrochemical station is needed and the operation cost is high

Table 1 Summary of advantages and disadvantages of preparation methods for SACs.

Preparation method	Advantage	Disadvantag
Wetness impregnation	simple to operate	metal atoms generally do not achieve uniform dispersion on the surface of the support
Ion exchange	enables the synthesis of highly loaded single atoms on the support surface	only applicable for the synthesis of limited types of SACs
Co-precipitation	suitable for the preparation of composite oxides with two or more uniformly dispersed metal elements	1. preparation parameters exert a significant influence on catalyst performance 2. a portion of active atoms remain unexposed and thus cannot participate in catalytic reactions
Templated hydrothermal	simple and easy to operate	same as ion exchange
Metal leaching	preparation of monodispersed catalysts by a two-step method	1. only suitable for a limited range of specific metals and support materials 2. the preparation process is associated with environmental pollution
Facile adsorption	simple and easy to operate	a proper interaction between the active metal components and the catalyst support is required
Strong electrostatic adsorption	suitable for the preparation of high-quality precious metal SACs	the adsorption behavior is influenced by multiple factors
Pyrolysis synthesis	facilitates straightforward preparation of SACs	demands a high pyrolysis temperature
Ball-milling	simple, scalable production, green	the catalysts are prone to agglomeration
Two-step doping	high stability	1. it is necessary to provide mobile atoms and a support capable of capturing mobile species 2. high-temperature synthesis necessitates a high-energy atom/ion generator
Host-guest strategy	1. strong stabilization of isolated atoms 2. tunable coordination environment	1. limited to supports with suitable porosity 2. complex synthesis routes
Photoreduction	the approach requires no specialized equipment and is straightforward to implement	the catalytic active centers are generally non-uniform
Atomic layer deposition	1. precise manipulation of process parameters 2. superior deposition uniformity and high reproducibility 3. the loading of singly dispersed atoms can be tailored by adjusting the number of deposition cycles	1. only support materials functionalized with appropriate ligands or functional groups are viable for selection 2. not amenable to large-scale commercial manufacturing
Atom trapping	the operation process is simple	same as two-step doping
One-pot wet chemistry	1. no specialized experimental setup or multi-step reaction conditions are required, which is conducive to large-scale production 2. high loading of isolated metal atoms can be achieved	limited by the solubility of different precursors
Cyclic voltammetry	less additives are demanded and no interfering products are generated	an electrochemical station is needed and the operation cost is high

Fig. 3. (a) HAADF-STEM image of 0.08% Pt/FeOx-R200. Reprinted with permission from Ref. [41]. Copyright 2014, Springer nature. (b) STM image of 0.02 ML Pt/Cu (111) SAA surface. Reprinted with permission from Ref. [77]. Copyright 2014, Springer nature. (c) Schematic illustration of the 0.2Pt/m-Al2O3-H2 synthesis process. Reprinted with permission from Ref. [78]. Copyright 2017, Springer nature. (d) Schematic synthetic illustration for constructing single-atom Pd supported on nanoscale TiO2. Reprinted with permission from Ref. [79]. Copyright 2020, Springer nature.

Fig. 4. (a) Promising candidates at different temperatures are highlighted in the figure. Reprinted with permission from Ref. [98]. Copyright 2021, Springer nature. (b) Stability of SAAs relative to competing configurations. Reprinted with permission from Ref. [99]. Copyright 2020, Springer nature. (c) Trapping energies of metal atoms, defined as the difference in the binding energies at the point defects and the ideal graphene or h-BN. Reprinted with permission from Ref. [102]. Copyright 2014, American Chemical Society.

Fig. 6. (a) Design scheme to promote homolysis of H2. Reprinted with permission from Ref. [111]. Copyright 2014, American Chemical Society. (b) Model of Pd1/C3N4 catalytic dechlorination of 4-chlorophenol. Reprinted with permission from Ref. [114]. Copyright 2020, American Chemical Society. (c) Model diagram of activation of hydrogen molecules catalyzed by Pt@Y. Reprinted with permission from Ref. [115]. Copyright 2021, American Chemical Society.

Table 2 The performance of noble metal SACs in selective hydrogenation reactions.

Catalyst	Reactant	Product	T (°C)	P (bar)	Conv. (%)	Sel. (%)	TOF (h^‒1)	Ref.
Pd₁/TiO₂	acetylene	ethylene	120	1	100	65	—	[116]
Pd₁-N8/CNT	acetylene	ethylene	40	1	83	98	1998	[117]
Pd₁/CeO₂	acetylene	ethylene	150	1	90	80.6	—	[118]
Z@Pd₁@Z	acetylene	ethylene	120	1	100	98.3	—	[119]
Pd₁/SiO₂-NH₂	acetylene	ethylene	190	1	100	92	18451.2	[120]
Pd/PPh₃-COF	acetylene	ethylene	80	1	90	95	86.4	[121]
Pd₁/G	phenylacetylene	styrene	25	1	100	94	267	[122]
Pd₁/Ni@G	phenylacetylene	styrene	30	2	100	93	7074	[123]
Pd₁/NC-PHF	phenylacetylene	styrene	60	5	93.1	93.5	139.1	[124]
Pd_0.2/TiO₂	phenylacetylene	styrene	25	10	99	91	8596	[79]
Pd₁+Pd_n@NC/HAP	2-methyl-3-butyn-2-ol	2-methyl-3-buten-2-ol	30	1	99	97.2	3707.7	[125]
Pd₁/TiO₂	acetophenone	1-phenylethanol	60	5	99.9	97.4	1571	[126]
Pd₁/α-MOC	4-nitrochlorobenzene	4-chloroaniline	60	5	100	99	2280	[127]
Pd/CHT-800	phenol	cyclohexanone	170	10	100	99.9	213.1	[128]
Pd₁/TiO₂	4-chlorophenol	cyclohexanone	25	1	100	95.63	95.05	[129]
Pd₁/CeO₂	4-chlorophenol	phenol	25	1	100	47.1	4.1	[130]
Pd₁/rGO	4-chlorophenol	phenol	25	1	—	100	—	[131]
Pd₁/C₃N₄	4-chlorophenol	phenol	90	1	99	99	146	[114]
Pd₁/C₃N₄	furfural	furfuryl alcohol	80	1	64	99	13333	[114]
Pd₁/α-MOC	furfural	furfuryl alcohol	80	10	96.7	92.4	—	[132]
Pd₁/SAPO-31	vanillin	vanillyl alcohol	80	1	99	99	3000	[133]
Pd₁/h-BN	cinnamaldehyde	cinnamyl alcohol	50	1	99	93	1112	[134]
Pt₁@Y	cinnamaldehyde	cinnamyl alcohol	130	30	100	92	— —	[115]
Pt₁@Y	2-nitrochlorobenzene	2-chloroaniline	100	20	100	99	— —	[115]
Pt/FeO_xH_y	propyne	propylene	120	1	—	94.1	9.4×10⁵	[135]
Pt₁/TiO₂-600	p-chloronitrobenzene	p-chloroaniline	80	15	100	99	—	[136]
Pt₁/CoAlO_x	furfural	furfuryl alcohol	25	1	100	99	—	[137]
Pt₁/Ti₃C₂T_x	formaldehyde	methanol	25	1	30.7	95.8	—	[138]
Pt₁/CeO₂	nitroarene	aromatic amines	70	1	45.4	99.7	198	[139]
Pt₁/NC	nitroarene	aromatic amines	30	10	99	99	9428.1	[140]
Pt₁/TiO₂	m-cresol	m-xylene	350	1	15	—	1	[141]
Pt₁/TiO₂	CO₂	CO	350	1	7.5	100	15	[142]
Rh₁CaAl-LDH	quinoline	1,2,3,4-tetrahydroquinoline	80	20	100	99	246	[143]
1Na-Rh/ZrO₂	CO₂	methyl formate	300	10	62	99	9.4	[144]
Rh₁/TiO₂@C₂NH₂PA	CO₂	CO	250	1	21	100	1020	[145]
Rh₁/TiO₂	CO₂	CO	500	1	3	96	—	[146]
Rh₁/CeTiO_x	CO₂	ethanol	250	30	6.3	99.1	493.1	[147]
Ru₁/In₂O₃-F	CO₂	methanol	290	50	12.9	74.02	671.4	[148]
0.6Ru-IPP_PF6	CO₂	methyl formate	120	30	25	99	166.7	[149]
Ru₁N₃	CO₂	CH₄	150	1	30	95	—	[150]
Ru₁N₃	CO	CH₄	150	1	99	95	—	[150]
Ru/CeO₂-S	aromatics	cyclohexanols	200	10	99.9	92.1	336.6	[151]
Ru₁/CeO₂	nitrobenzene	aniline	120	20	17.9	88.2	—	[152]
Ir₁₊_n_p/CMK	quinoline	1,2,3,4-tetrahydroquinoline	100	20	—	99	7800	[153]

Table 2 The performance of noble metal SACs in selective hydrogenation reactions.

Catalyst	Reactant	Product	T (°C)	P (bar)	Conv. (%)	Sel. (%)	TOF (h^‒1)	Ref.
Pd₁/TiO₂	acetylene	ethylene	120	1	100	65	—	[116]
Pd₁-N8/CNT	acetylene	ethylene	40	1	83	98	1998	[117]
Pd₁/CeO₂	acetylene	ethylene	150	1	90	80.6	—	[118]
Z@Pd₁@Z	acetylene	ethylene	120	1	100	98.3	—	[119]
Pd₁/SiO₂-NH₂	acetylene	ethylene	190	1	100	92	18451.2	[120]
Pd/PPh₃-COF	acetylene	ethylene	80	1	90	95	86.4	[121]
Pd₁/G	phenylacetylene	styrene	25	1	100	94	267	[122]
Pd₁/Ni@G	phenylacetylene	styrene	30	2	100	93	7074	[123]
Pd₁/NC-PHF	phenylacetylene	styrene	60	5	93.1	93.5	139.1	[124]
Pd_0.2/TiO₂	phenylacetylene	styrene	25	10	99	91	8596	[79]
Pd₁+Pd_n@NC/HAP	2-methyl-3-butyn-2-ol	2-methyl-3-buten-2-ol	30	1	99	97.2	3707.7	[125]
Pd₁/TiO₂	acetophenone	1-phenylethanol	60	5	99.9	97.4	1571	[126]
Pd₁/α-MOC	4-nitrochlorobenzene	4-chloroaniline	60	5	100	99	2280	[127]
Pd/CHT-800	phenol	cyclohexanone	170	10	100	99.9	213.1	[128]
Pd₁/TiO₂	4-chlorophenol	cyclohexanone	25	1	100	95.63	95.05	[129]
Pd₁/CeO₂	4-chlorophenol	phenol	25	1	100	47.1	4.1	[130]
Pd₁/rGO	4-chlorophenol	phenol	25	1	—	100	—	[131]
Pd₁/C₃N₄	4-chlorophenol	phenol	90	1	99	99	146	[114]
Pd₁/C₃N₄	furfural	furfuryl alcohol	80	1	64	99	13333	[114]
Pd₁/α-MOC	furfural	furfuryl alcohol	80	10	96.7	92.4	—	[132]
Pd₁/SAPO-31	vanillin	vanillyl alcohol	80	1	99	99	3000	[133]
Pd₁/h-BN	cinnamaldehyde	cinnamyl alcohol	50	1	99	93	1112	[134]
Pt₁@Y	cinnamaldehyde	cinnamyl alcohol	130	30	100	92	— —	[115]
Pt₁@Y	2-nitrochlorobenzene	2-chloroaniline	100	20	100	99	— —	[115]
Pt/FeO_xH_y	propyne	propylene	120	1	—	94.1	9.4×10⁵	[135]
Pt₁/TiO₂-600	p-chloronitrobenzene	p-chloroaniline	80	15	100	99	—	[136]
Pt₁/CoAlO_x	furfural	furfuryl alcohol	25	1	100	99	—	[137]
Pt₁/Ti₃C₂T_x	formaldehyde	methanol	25	1	30.7	95.8	—	[138]
Pt₁/CeO₂	nitroarene	aromatic amines	70	1	45.4	99.7	198	[139]
Pt₁/NC	nitroarene	aromatic amines	30	10	99	99	9428.1	[140]
Pt₁/TiO₂	m-cresol	m-xylene	350	1	15	—	1	[141]
Pt₁/TiO₂	CO₂	CO	350	1	7.5	100	15	[142]
Rh₁CaAl-LDH	quinoline	1,2,3,4-tetrahydroquinoline	80	20	100	99	246	[143]
1Na-Rh/ZrO₂	CO₂	methyl formate	300	10	62	99	9.4	[144]
Rh₁/TiO₂@C₂NH₂PA	CO₂	CO	250	1	21	100	1020	[145]
Rh₁/TiO₂	CO₂	CO	500	1	3	96	—	[146]
Rh₁/CeTiO_x	CO₂	ethanol	250	30	6.3	99.1	493.1	[147]
Ru₁/In₂O₃-F	CO₂	methanol	290	50	12.9	74.02	671.4	[148]
0.6Ru-IPP_PF6	CO₂	methyl formate	120	30	25	99	166.7	[149]
Ru₁N₃	CO₂	CH₄	150	1	30	95	—	[150]
Ru₁N₃	CO	CH₄	150	1	99	95	—	[150]
Ru/CeO₂-S	aromatics	cyclohexanols	200	10	99.9	92.1	336.6	[151]
Ru₁/CeO₂	nitrobenzene	aniline	120	20	17.9	88.2	—	[152]
Ir₁₊_n_p/CMK	quinoline	1,2,3,4-tetrahydroquinoline	100	20	—	99	7800	[153]

Fig. 7. (a) Ethylene selectivity as a function of temperature for acetylene semi-hydrogenation over Pd/TiO2-200H and Pd/TiO2-600H. Reprinted with permission from Ref. [116]. Copyright 2022, Springer nature. (b) Ethylene selectivity as a function of temperature for selective hydrogenation of acetylene in excess ethylene over different samples. Reprinted with permission from Ref. [118]. Copyright 2022, Springer nature. (c) Magnetic property test for Pd1/Ni@G with an external magnetic field. Reprinted with permission from Ref. [123]. Copyright 2022, John Wiley and Sons. (d) The cycle performance of Pd1/NC-PHF. Reprinted with permission from Ref. [124]. Copyright 2023, Elsevier.

Fig. 8. (a) Comparison of the activities of Pd1/TiO2 and Pdn/TiO2 at different temperatures. Reprinted with permission from Ref. [126]. Copyright 2023, American Chemical Society. (b) Conversion and product selectivity over various Pd-containing catalysts. Reprinted with permission from Ref. [127]. Copyright 2020, John Wiley and Sons. (c) The yield and selectivity of CYC via reaction time. Reprinted with permission from Ref. [129]. Copyright 2025, Elsevier. (d) Illustrates electron density differences, activation energy, and migration energy of hydrogen on different models about Pd SACs. Reprinted with permission from Ref. [132]. Copyright 2024, John Wiley and Sons.

Fig. 9. (a) The hydrogenation of various halogenated nitrobenzenes over Pt1/TiO2-600. Reprinted with permission from Ref. [136]. Copyright 2024, John Wiley and Sons. (b) Reaction mechanism of FAL hydrogenation to FOL or THFOL over Pt1/CoAlOx or Ptn/CoAlOx, respectively. Reprinted with permission from Ref. [137]. Copyright 2023, American Chemical Society. (c) Conversion and selectivity of trans-β-nitrostyrene hydrogenation over Pt1/CeO2 catalyst in recycling tests. Reprinted with permission from Ref. [139]. Copyright 2022, Springer nature. (d) A schematic illustration of the regulation of Rh1-ZrO2 cooperativity by Na ions for selectivity tuning. Reprinted with permission from Ref. [144]. Copyright 2023, John Wiley and Sons. (e) CO2 conversion and product distribution. Reprinted with permission from Ref. [145]. Copyright 2023, American Chemical Society. (f) Selective hydrogenation reaction equation for dearomatization of aromatics. Reprinted with permission from Ref. [147]. Copyright 2022, John Wiley and Sons.

Table 3 The performance of non-noble metal SACs in selective hydrogenation reactions.

Catalyst	Reactant	Product	T (°C)	P (bar)	Conv. (%)	Sel. (%)	TOF (h^‒1)	Ref.
Co₁/@Y	acetylene	ethylene	220	1	90	93	—	[56]
Co-N₄P₁	halonitrobenzene	haloanilines	80	5	83.2	99	—	[61]
Co₃N₄-S	p-chloronitrobenzene	p-chloroaniline	80	10	94.5	90.7	—	[164]
Co₁/NC	nitrocompounds	aminocompounds	100	5	100	100	—	[55]
Co/SBA-15	CO₂	CO	600	1	37	99	304.6	[165]
Co/C-PAQ	nitrobenzene	aniline	80	10	99	99	398	[166]
Co₁/Co_n@NCNS	nitroarenes	aromatic amines	50	10	99	99	—	[167]
Co-NAC	nitroarenes	aromatic amines	80	20	99	99	19.7	[168]
Co₁/NPC	nitroarenes	aromatic amines	110	30	99	99	6560	[169]
Co₁-N/P-C	p-chloronitrobenzene	p-chloroaniline	100	20	99	99	241.5	[170]
Co₁/NC	nitrobenzene	aniline	110	30	99.7	99.1	76.8	[171]
Co@N_x-C-800	nitroarenes	aromatic amines	120	15	100	99	317.7	[172]
Co-N₄/TiN-rGO	4-nitrophenol	4-aminophenol	25	1	99	99	—	[173]
Co₁@NC-(SBA)	vanillin	vanillyl alcohol	140	10	100	99.2	—	[174]
Co₁@NC-(SBA)	p-nitrochlorobenzene	p-chloroaniline	90	10	100	99	—	[174]
Co₁@NHOPC	quinoline	1,2,3,4-tetrahydroquinoline	100	20	100	99	—	[175]
Cu₁/CN/TiO₂	quinoline	1,2,3,4-tetrahydroquinoline	60	1	94	99	104	[176]
Cu₁/NC	acetylene	ethylene	25	1	—	97	—	[54]
Cu₁/CN	phenylacetylene	styrene	70	1	94	99	74	[177]
Cu₁/TiO₂	2-butyne-1,4-diol	2-butene-1,4-diol	25	1	100	99.4	—	[178]
Fe-ZIF-800	furfural	furfuryl alcohol	120	1	99.5	96.9	1882	[60]
Fe-N/S-C	nitroarenes	aromatic amines	25	1	100	99	116.9	[179]
Fe₁/N-C	nitroarenes	aromatic amines	60	1	100	99	748	[180]
Fe₁/N-C	nitrobenzene	aniline	160	5	99	99	—	[181]
Mo/NC	CO₂	CO	500	0.69	30.4	100	80	[182]
Ni₁/Bi₃O₄Br	CO₂	CH₄	40	0.95	—	95.1	—	[183]
Ni₁-Ni_x/C_v	acetylene	ethylene	240	1	95.26	93.5	—	[184]
Ni₁-N₃/C	acetylene	ethylene	220	1	100	94	—	[185]
Ni SAs-N@LC	vanillin	vanillyl alcohol	180	1	98.93	97.3	—	[186]
Ni₁/TiO₂	cinnamaldehyde	cinnamyl alcohol	130	30	98	90	102	[187]
Ni₁@Beta	furfural	furfuryl alcohol	110	10	93.7	97.5	114.1	[188]
Ni₁/NC	furfural	furfuryl alcohol	100	1	99	99	2908.1	[189]

Table 3 The performance of non-noble metal SACs in selective hydrogenation reactions.

Catalyst	Reactant	Product	T (°C)	P (bar)	Conv. (%)	Sel. (%)	TOF (h^‒1)	Ref.
Co₁/@Y	acetylene	ethylene	220	1	90	93	—	[56]
Co-N₄P₁	halonitrobenzene	haloanilines	80	5	83.2	99	—	[61]
Co₃N₄-S	p-chloronitrobenzene	p-chloroaniline	80	10	94.5	90.7	—	[164]
Co₁/NC	nitrocompounds	aminocompounds	100	5	100	100	—	[55]
Co/SBA-15	CO₂	CO	600	1	37	99	304.6	[165]
Co/C-PAQ	nitrobenzene	aniline	80	10	99	99	398	[166]
Co₁/Co_n@NCNS	nitroarenes	aromatic amines	50	10	99	99	—	[167]
Co-NAC	nitroarenes	aromatic amines	80	20	99	99	19.7	[168]
Co₁/NPC	nitroarenes	aromatic amines	110	30	99	99	6560	[169]
Co₁-N/P-C	p-chloronitrobenzene	p-chloroaniline	100	20	99	99	241.5	[170]
Co₁/NC	nitrobenzene	aniline	110	30	99.7	99.1	76.8	[171]
Co@N_x-C-800	nitroarenes	aromatic amines	120	15	100	99	317.7	[172]
Co-N₄/TiN-rGO	4-nitrophenol	4-aminophenol	25	1	99	99	—	[173]
Co₁@NC-(SBA)	vanillin	vanillyl alcohol	140	10	100	99.2	—	[174]
Co₁@NC-(SBA)	p-nitrochlorobenzene	p-chloroaniline	90	10	100	99	—	[174]
Co₁@NHOPC	quinoline	1,2,3,4-tetrahydroquinoline	100	20	100	99	—	[175]
Cu₁/CN/TiO₂	quinoline	1,2,3,4-tetrahydroquinoline	60	1	94	99	104	[176]
Cu₁/NC	acetylene	ethylene	25	1	—	97	—	[54]
Cu₁/CN	phenylacetylene	styrene	70	1	94	99	74	[177]
Cu₁/TiO₂	2-butyne-1,4-diol	2-butene-1,4-diol	25	1	100	99.4	—	[178]
Fe-ZIF-800	furfural	furfuryl alcohol	120	1	99.5	96.9	1882	[60]
Fe-N/S-C	nitroarenes	aromatic amines	25	1	100	99	116.9	[179]
Fe₁/N-C	nitroarenes	aromatic amines	60	1	100	99	748	[180]
Fe₁/N-C	nitrobenzene	aniline	160	5	99	99	—	[181]
Mo/NC	CO₂	CO	500	0.69	30.4	100	80	[182]
Ni₁/Bi₃O₄Br	CO₂	CH₄	40	0.95	—	95.1	—	[183]
Ni₁-Ni_x/C_v	acetylene	ethylene	240	1	95.26	93.5	—	[184]
Ni₁-N₃/C	acetylene	ethylene	220	1	100	94	—	[185]
Ni SAs-N@LC	vanillin	vanillyl alcohol	180	1	98.93	97.3	—	[186]
Ni₁/TiO₂	cinnamaldehyde	cinnamyl alcohol	130	30	98	90	102	[187]
Ni₁@Beta	furfural	furfuryl alcohol	110	10	93.7	97.5	114.1	[188]
Ni₁/NC	furfural	furfuryl alcohol	100	1	99	99	2908.1	[189]

Fig. 10. (a) Ethylene selectivity as a function of temperature of Co1@Y and Co/Y under the same reaction conditions. (b) Reaction mechanism of acetylene selective hydrogenation over Co1@Y. Reprinted with permission from Ref. [56]. Copyright 2025, American Chemical Society. (c) The catalytic performance of various catalysts for the p-NB selective hydrogenation. Reprinted with permission from Ref. [61]. Copyright 2024, John Wiley and Sons. (d) Catalytic performance of various Co-SACs in the hydrogenation of p-CNB under H2 atmospheres. Reprinted with permission from Ref. [164]. Copyright 2024, American Chemical Society. (e) Hydrogenation activity test of Co1/NC, Co/NC, and NC. Reprinted with permission from Ref. [55]. Copyright 2024, Springer nature. (f) Stability of Co/SBA-15. Reprinted with permission from Ref. [165]. Copyright 2022, Elsevier.

Fig. 11. (a) Proposed mechanism for heterolytic cleavage of H2 via the proticsolvent-mediated H-shuttling mechanism on the homogeneous catalyst and Co/C-PAQ. Reprinted with permission from Ref. [166]. Copyright 2022, American Chemical Society. (b) Catalytic results of the 3-nitrostyrene hydrogenation over Co-100-NAC in the presence of S-containing reagents. Reprinted with permission from Ref. [168]. Copyright 2022, Springer nature. (c) Electron-density isosurface of Co atoms in two models. Blue: positive, red: negative. Reprinted with permission from Ref. [169]. Copyright 2022, Springer nature. (d) Catalytic performance of N/P-C, Co1-N-C, Co1-N/P-C, and Pt/C for p-CNB hydrogenation. Reprinted with permission from Ref. [170]. Copyright 2024, Elsevier. (e) Effect of water on the selective hydrogenation of nitrobenzene over Co SAs/NC. Reprinted with permission from Ref. [171]. Copyright 2020, American Chemical Society.

Fig. 12. (a) Long-term stability of Cu SA/NC at a current density load of ?100 mA cm?2 and the corresponding FEs of C2H4, C4H6 and H2. Reprinted with permission from Ref. [54]. Copyright 2023, John Wiley and Sons. (b) Recycling test of Cu1/CN/Al2O3 for transfer hydrogenation of phenylacetylene. Reprinted with permission from Ref. [177]. Copyright 2010, Royal Society of Chemistry. (c) Schematic illustration of the photocatalytic BYD semi-hydrogenation path on Cu-SAs-TiO2. Reprinted with permission from Ref. [178]. Copyright 2025, American Chemical Society.

Fig. 13. (a) Bader charge transfer numbers of Fe-N3S1 and Fe-N4. Reprinted with permission from Ref. [179]. Copyright 2025, Elsevier. (b) Energy profiles of the hydrogenation from PhNO2 to PhNH2 on Fe-N4. Reprinted with permission from Ref. [180]. Copyright 2019, American Chemical Society. (c) TOF and production distribution of Mo/NC catalysts versus Mo loading. Reprinted with permission from Ref. [182]. Copyright 2022, John Wiley and Sons. (d) Performance comparison of different heterogeneous catalysts for the selective hydrogenation of cinnamaldehyde. Reprinted with permission from Ref. [187]. Copyright 2022, John Wiley and Sons.

Fig. 14. Conversion and selectivity of different single-metal SACs toward specific substances in hydrogenation reactions.

Table 4 The performance of bimetallic SACs in selective hydrogenation reactions.

Catalyst	Reactant	Product	T (°C)	P (bar)	Conv. (%)	Sel. (%)	Ref.
Cu₁Au_n/NU-1000	CO₂	C₂H₆	25	1	69.9	71.1	[191]
Co₁Cu₁/PHI	CO₂	formic acid	300	35	—	75	[192]
Zn₁Pd_n/OC/Al₂O₃	p-iodonitrobenzene	p-iodoaniline	80	1	94	100	[193]
Ru₁Ni_n/CNT	cinnamaldehyde	cinnamyl alcohol	160	20	74.1	90	[194]
Pd_n/Ni₁@γ-Al₂O₃	phenylacetylene	styrene	25	1	98	94	[195]
Cu₁Pt_n	epichlorohydrin	3-chloro-1-propanol	90	40	98	92	[196]
Pd₁Cu₁/ND@G	acetylene	ethylene	110	1	100	92	[197]
Ru₁Cu_n/SiO₂	acetylene	ethylene	170	1	100	97.6	[198]
Ag₁Cu₁-C₃N₄	alkyne	olefin	25	1	99	99	[199]
h-Pd₁Mn₁/NC	phenylacetylene	styrene	60	15	99	95	[200]
PdRu-ZPO	phenylacetylene	styrene	60	20	97	91	[201]
Ir₁Mo₁/TiO₂	4-nitrostyrene	4-aminostyrene	120	20	100	96.3	[52]
Ni_0.5Co_0.5-MOF	4-chloronitrobenzene	4-chloroaniline	25	1	99.9	99.1	[202]
Pt₁Fe₁/ND	p-nitrochlorobenzene	p-chloroaniline	80	10	100	99	[203]
Pt₁Co₁-CeO₂	CO₂	CO	400	1	22.5	98.5	[204]
Pt₁Ni₁-CeO₂	CO₂	CO	400	1	16	96.5	[204]

Fig. 15. (a) Schematic illustration of the tannic acid coating-confinement strategy. Reprinted with permission from Ref. [193]. Copyright 2022, John Wiley and Sons. (b) Stability cyclic test of Pd0.5/Ni0.5@γ-Al2O3. Reprinted with permission from Ref. [194]. Copyright 2023, Elsevier. (c) Schematic illustration of possible reaction pathway for the catalytic hydrogenation of epichlorohydrin. Reprinted with permission from Ref. [196]. Copyright 2023, Elsevier.

Fig. 16. (a) C2H2 conversion rate and C2H4 selectivity as a function of temperature over Pd1Cu1 DSAC. Reprinted with permission from Ref. [197]. Copyright 2022, American Chemical Society. (b) Stability test of h-Pd-Mn/NC. Reprinted with permission from Ref. [200]. Copyright 2024, American Chemical Society. (c) Pd/Ru ratio dependence of the conversion and selectivity of the phenylacetylene semi-hydrogenation. Reprinted with permission from Ref. [201]. Copyright 2021, Royal Society of Chemistry. (d) Schematic illustration of the construction of 2D NiCo-MOF bimetallic nanosheets for selective reduction of nitroarenes. Reprinted with permission from Ref. [202]. Copyright 2014, Royal Society of Chemistry. (e) dual single-atoms on CeO2?x support. Reprinted with permission from Ref. [204]. Copyright 2025, Elsevier.

Table 5 The performance of SAAs in selective hydrogenation reactions.

Catalyst	Reactant	Product	T (°C)	P (bar)	Conv. (%)	Sel. (%)	Ref.
Pd₁Au	1-hexyne	1-hexene	100	0.2	10.6	98	[205]
Pd₁/NiGa	acetylene	ethylene	110	1	100	95	[206]
Pd₁/NiGa	propyne	propylene	110	1	95	98	[206]
Pd₁Fe	phenylacetylene	styrene	25	1	99.9	96	[207]
Pd₁Ni/SiO₂	acetylene	ethylene	80	1	100	88	[208]
Pd₁/Cu	1,3-butadiene	1-butene	106.9	0.01	100	84	[209]
Ru₁Ni	4-nitrostyrene	4-aminostyrene	60	10	100	99	[210]
Ir₁Ni	4-nitrostyrene	4-aminostyrene	50	10	100	98	[211]
IrCu₁/C	p-bromonitrobenzene	p-bromoaniline	80	10	100	99	[212]
Pd₁Ag₁₀/Al₂O₃	diphenylacetylene	cis-stilbene	25	5	100	99	[213]
CuPd₁/Al₂O₃	furfural	furfuryl alcohol	220	1	99.9	81	[214]
Pd₁Cu/Al₂O₃	furfural	furfuryl alcohol	50	1.5	40.1	99.1	[215]
Pt₁Cu	furfural	furfuryl alcohol	50	20	100	99	[216]
Ru₁Cu	5-hydroxymethylfurfural	5-hydroxymethylfurfuryl alcohol	25	1	65.9	89.4	[217]
Pt₁/Co	5-hydroxymethylfurfural	5-hydroxymethylfurfuryl alcohol	180	10	100	92.9	[218]
Pd₁Cu	crotonaldehyde	crotyl alcohol	50	1.5	99	84.3	[219]

Fig. 17. (a) Schematic representation of the course of 1-hexyne hydrogenation. Reprinted with permission from Ref. [205]. Copyright 2022, American Chemical Society. (b) high-resolution AC-HAADF-STEM image of RuNi SAA catalyst. (c) Reusability tests of Ru1Ni catalyst within five successive catalytic cycles. Reprinted with permission from Ref. [210]. Copyright 2022, Springer nature. (d) Reusability tests of Ir1Ni catalyst within five successive catalytic cycles. Reprinted with permission from Ref. [211]. Copyright 2024, John Wiley and Sons.

Fig. 18. (a) Reaction pathway of the conversion of FF to 2-MF on Cu8Pd1/Al2O3 catalyst. Reprinted with permission from Ref. [214]. Copyright 2025, John Wiley and Sons. (b) The reaction profiles of furfural conversion and selectivity [215]. Reprinted with permission from Ref. [215]. Copyright 2021, Elsevier. (c) Reactivity of the PtCu catalysts used at 20 bar. Reprinted with permission from Ref. [216]. Copyright 2021, Elsevier. (d) Proposed electrochemical reduction mechanism of HMF over Ru1Cu. Reprinted with permission from Ref. [217]. Copyright 2022, John Wiley and Sons.

Fig. 19. Challenges faced by SACs.

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Towards highly efficient selective hydrogenation: The role of single-atom catalysts

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