Efficient CO2 photoreduction towards C2+ solar fuels has emerged as one of the most promising strategies for alleviating the current energy and environment problems. However, the C-C coupling barriers and complex multi-electron transfer steps still limit the activity and selectivity of CO2-to-C2 photoreduction. Herein, Au nanoparticles (NPs) modified CeO2 with oxygen vacancies (Au/CeO2-VO) were reported for enhancing the CO2-to-C2H6 photoreduction performance. Au/CeO2-VO achieved the high C2H6 activity of 51.7 μmol·g−1·h−1, accompanied with C2H6 selectivity up to 80% in the absence of sacrificial agent. Experimental results combined with theoretical simulation indicated that VO strengthened CO2 adsorption and activated *CO production, and plasmon-induced hot electrons from Au NPs to CeO2-VO facilitated the *CO-*CO dimerization. The synergistic modulation of VO and hot electrons further decreased the energy barriers of C-C coupling and subsequent hydrogenation, resulting in the superior photoreduction performance. This work opens an avenue of developing plasmonic photocatalysts for multi-carbon products from CO2 photoreduction.
Zhang, M. R.; Zhang, D.; Jing, X.; Xu, B. J.; Duan, C. Y. Engineering NH2–Cu–NH2 triple-atom sites in defective MOFs for selective overall photoreduction of CO2 into CH3COCH3. Angew. Chem., Int. Ed. 2024, 63, e202402755.
Xie, Z. K.; Xu, S. J.; Li, L. H.; Gong, S. H.; Wu, X. J.; Xu, D. B.; Mao, B. D.; Zhou, T.; Chen, M.; Wang, X. et al. Well-defined diatomic catalysis for photosynthesis of C2H4 from CO2. Nat. Commun. 2024, 15, 2422.
Wang, L. G.; Wu, J. B.; Wang, S. W.; Liu, H.; Wang, Y.; Wang, D. S. The reformation of catalyst: From a trial-and-error synthesis to rational design. Nano Res. 2024, 17, 3261–3301.
Fang, J. J.; Zhu, C. Y.; Hu, H. L.; Li, J. Q.; Li, L. C.; Zhu, H. Y.; Mao, J. J. Progress of photocatalytic CO2 reduction toward multi-carbon products. Sci. China Chem. 2024, 67, 3994–4013.
Mu, X. Q.; Liu, S. L.; Zhang, M. Y.; Zhuang, Z. C.; Chen, D.; Liao, Y. R.; Zhao, H. Y.; Mu, S. C.; Wang, D. S.; Dai, Z. H. Symmetry-broken Ru nanoparticles with parasitic Ru–Co dual-single atoms overcome the volmer step of alkaline hydrogen oxidation. Angew. Chem. 2024, 136, e202319618.
Ban, C. G.; Wang, Y.; Feng, Y. J.; Zhu, Z. H.; Duan, Y. Y.; Ma, J. P.; Zhang, X.; Liu, X.; Zhou, K.; Zou, H. J. et al. Photochromic single atom Ag/TiO2 catalysts for selective CO2 reduction to CH4. Energy Environ. Sci. 2024, 17, 518–530.
Di, J.; Chen, C.; Wu, Y.; Chen, H.; Xiong, J.; Long, R.; Li, S. Z.; Song, L.; Jiang, W.; Liu, Z. Asymmetric electron redistribution in niobic-oxygen vacancy associates to tune noncovalent interaction in CO2 photoreduction. Adv. Mater. 2024, 36, 2401914.
Zhang, Y.; Mu, X. Q.; Liu, Z. Y.; Zhao, H. Y.; Zhuang, Z. C.; Zhang, Y. F.; Mu, S. C.; Liu, S. L.; Wang, D. S.; Dai, Z. H. Twin-distortion modulated ultra-low coordination PtRuNi–O x catalyst for enhanced hydrogen production from chemical wastewater. Nat. Commun. 2024, 15, 10149.
Tao, Y.; Guan, J. P.; Zhang, J.; Hu, S. Y.; Ma, R. Z.; Zheng, H. R.; Gong, J. X.; Zhuang, Z. C.; Liu, S. J.; Ou, H. H. et al. Ruthenium single atomic sites surrounding the support pit with exceptional photocatalytic activity. Angew. Chem., Int. Ed. 2024, 63, e202400625.
Wang, L.; Wang, L.; Xu, Y. K.; Sun, G. X.; Nie, W. C.; Liu, L. H.; Kong, D. B.; Pan, Y.; Zhang, Y. H.; Wang, H. et al. Schottky junction and D–A1–A2 system dual regulation of covalent triazine frameworks for highly efficient CO2 photoreduction. Adv. Mater. 2024, 36, 2309376.
Ning, S. B.; Ou, H. H.; Li, Y. G.; Lv, C. C.; Wang, S. F.; Wang, D. S.; Ye, J. H. Co0–Co δ + Interface double-site-mediated C–C coupling for the photothermal conversion of CO2 into light olefins. Angew. Chem., Int. Ed. 2023, 62, e202302253.
Zhang, M. Y.; Zhou, D. Y.; Mu, X. Q.; Wang, D. S.; Liu, S. L.; Dai, Z. H. Regulating the critical intermediates of dual-atom catalysts for CO2 electroreduction. Small 2024, 20, 2402050.
Fang, J. J.; Zhu, C. Y.; Fang, L. C.; Chen, Y. K.; Hu, H. L.; Wu, Y.; Chen, Q. Q.; Mao, J. J. Efficient charge relay steering in Pd nanoparticles coupled with the heterojunction for boosting CO2 photoreduction to C2H6. Sci. China Mater. 2024, 67, 2949–2956.
Wang, G.; Chen, Z.; Wang, T.; Wang, D. S.; Mao, J. J. P and Cu dual sites on graphitic carbon nitride for photocatalytic CO2 reduction to hydrocarbon fuels with high C2H6 evolution. Angew. Chem., Int. Ed. 2022, 134, e202210789.
Xu, R.; Si, D. H.; Zhao, S. S.; Wu, Q. J.; Wang, X. S.; Liu, T. F.; Zhao, H.; Cao, R.; Huang, Y. B. Tandem photocatalysis of CO2 to C2H4 via a synergistic rhenium-(I) bipyridine/copper-porphyrinic triazine framework. J. Am. Chem. Soc. 2023, 145, 8261–8270.
Wang, G.; Wu, Y.; Li, Z. J.; Lou, Z. Z.; Chen, Q. Q.; Li, Y. F.; Wang, D. S.; Mao, J. J. Engineering a copper single-atom electron bridge to achieve efficient photocatalytic CO2 conversion. Angew. Chem., Int. Ed. 2023, 62, e202218460.
Zhang, Y. D.; Sun, Y. J.; Wang, Q. Y.; Zhuang, Z. C.; Ma, Z. T.; Liu, L. M.; Wang, G. M.; Wang, D. S.; Zheng, X. S. Synergy of photogenerated electrons and holes toward efficient photocatalytic urea synthesis from CO2 and N2. Angew. Chem., Int. Ed. 2024, 63, e202405637.
Hu, Q. Y.; Li, M. Q.; Zhu, J. C.; Zhang, Z. X.; He, D. P.; Zheng, K.; Wu, Y.; Fan, M. H.; Zhu, S.; Yan, W. S. et al. Nitrogen doping-roused synergistic active sites in perovskite enabling highly selective CO2 photoreduction into CH4. Nano Lett. 2024, 24, 4610–4617.
Wang, Y.; Ma, F. Y.; Zhang, G. Q.; Zhang, J. W.; Zhao, H.; Dong, Y. M.; Wang, D. S. Precise synthesis of dual atom sites for electrocatalysis. Nano Res. 2024, 17, 9397–9427.
Yu, J.; Qin, X. T.; Yang, Y. S.; Lv, M. X.; Yin, P.; Wang, L.; Ren, Z.; Song, B. Y.; Li, Q.; Zheng, L. R. et al. Highly stable Pt/CeO2 catalyst with embedding structure toward water–gas shift reaction. J. Am. Chem. Soc. 2024, 146, 1071–1080.
Luo, L.; Fu, L.; Liu, H. F.; Xu, Y. X.; Xing, J. L.; Chang, C. R.; Yang, D. Y.; Tang, J. W. Synergy of Pd atoms and oxygen vacancies on In2O3 for methane conversion under visible light. Nat. Commun. 2022, 13, 2930.
Sun, Y. Y.; Ji, H. Q.; Sun, Y. J.; Zhang, G. X.; Zhou, H. J.; Cao, S.; Liu, S. X.; Zhang, L.; Li, W. T.; Zhu, X. W. et al. Synergistic effect of oxygen vacancy and high porosity of nano MIL-125(Ti) for enhanced photocatalytic nitrogen fixation. Angew. Chem., Int. Ed. 2024, 63, e202316973.
Luo, X.; Zhao, L. X.; Zhou, H. J.; He, L.; Lei, X.; Guan, Q. Q.; Liu, Z. L. Oxygen vacancy induction strategy to regulate the evolution of valence- and free-electrons for boosting visible photodegradation of tetracycline hydrochloride. J. Hazard. Mater. 2024, 466, 133624.
Liu, B. Y.; Zhang, B. G.; Liu, B. Y.; Hu, Z. F.; Dai, W. J.; Zhang, J. R.; Feng, F. D.; Lan, B.; Zhang, T.; Huang, H. B. Surface hydroxyl and oxygen vacancies engineering in ZnSnAl LDH: Synergistic promotion of photocatalytic oxidation of aromatic VOCs. Environ. Sci. Technol. 2024, 58, 4404–4414.
Yang, S. Y.; Zhang, W. S.; Pan, G. L.; Chen, J. Y.; Deng, J. Y.; Chen, K.; Xie, X. L.; Han, D. X.; Dai, M. J.; Niu, L. Photocatalytic Co-reduction of N2 and CO2 with CeO2 catalyst for urea synthesis. Angew. Chem., Int. Ed. 2023, 62, e202312076.
Tang, Z.; Li, Y. J.; Zhang, K. X.; Wang, X. X.; Wang, S. Y.; Sun, Y. F.; Zhang, H. Y.; Li, S. Y.; Wang, J. R.; Gao, X. Y. et al. Interfacial hydrogen spillover on Pd–TiO2 with oxygen vacancies promotes formate electrooxidation. ACS Energy Lett. 2023, 8, 3945–3954.
Han, W.; Chen, Y. J.; Jiao, Y. Z.; Liang, S. M.; Li, W.; Tian, G. H. Oxygen vacancy-rich S-scheme CeO2@Ni1− x Co x Se2 hollow spheres derived from NiCo–MOF for remarkable photocatalytic CO2 conversion. ACS Sustain. Chem. Eng. 2023, 11, 7787–7797.
Hao, L.; Huang, H. W.; Zhang, Y. H.; Ma, T. Y. Oxygen vacant semiconductor photocatalysts. Adv. Funct. Mater. 2021, 31, 2100919.
Hou, T. L.; Li, X. Y.; Zhang, X. M.; Cai, R. S.; Wang, Y. C.; Chen, A. K.; Gu, H. F.; Su, M. Y.; Li, S. Y.; Li, Q. Z. et al. Atomic Au3Cu palisade interlayer in core@shell nanostructures for efficient Kirkendall effect mediation. Nano Lett. 2024, 24, 2719–2726.
Shangguan, W. C.; Liu, Q.; Wang, Y.; Sun, N.; Liu, Y.; Zhao, R.; Li, Y. X.; Wang, C. Y.; Zhao, J. C. Molecular-level insight into photocatalytic CO2 reduction with H2O over Au nanoparticles by interband transitions. Nat. Commun. 2022, 13, 3894.
Jiang, J. W.; Wang, X. F.; Guo, H. Enhanced interfacial charge transfer/separation by LSPR-induced defective semiconductor toward high CO2RR performance. Small 2023, 19, 2301280.
Li, X. Y.; Li, C.; Xu, Y. X.; Liu, Q.; Bahri, M.; Zhang, L. Q.; Browning, N. D.; Cowan, A. J.; Tang, J. W. Efficient hole abstraction for highly selective oxidative coupling of methane by Au-sputtered TiO2 photocatalysts. Nat. Energy 2023, 8, 1013–1022.
Zhang, S. C.; Chen, D.; Chen, P. G.; Zhang, R.; Hou, Y.; Guo, Y.; Li, P.; Liang, X.; Xing, T. Y.; Chen, J. et al. Concurrent mechanisms of hot electrons and interfacial water molecule ordering in plasmon-enhanced nitrogen fixation. Adv. Mater. 2024, 36, 2310776.
Zhao, J. Q.; Bai, Y.; Li, Z. H.; Liu, J. J.; Wang, W.; Wang, P.; Yang, B.; Shi, R.; Waterhouse, G. I. N.; Wen, X. D. et al. Plasmonic Cu nanoparticles for the low-temperature photo-driven water–gas shift reaction. Angew. Chem., Int. Ed. 2023, 62, e202219299.
Tang, J. L.; Li, Y. L.; Ye, S.; Jiang, P. Z.; Xue, Z. H.; Li, X. F.; Lyu, X. Y.; Liu, Q. Y.; Chu, S. S.; Yang, H. et al. Direct hot-electron transfer at the Au nanoparticle/monolayer transition-metal dichalcogenide interface observed with ultrahigh spatiotemporal resolution. Nano Lett. 2024, 24, 2931–2938.
Dey, A.; Mendalz, A.; Wach, A.; Vadell, R. B.; Silveira, V. R.; Leidinger, P. M.; Huthwelker, T.; Shtender, V.; Novotny, Z.; Artiglia, L. et al. Hydrogen evolution with hot electrons on a plasmonic-molecular catalyst hybrid system. Nat. Commun. 2024, 15, 445.
Meng, L. J.; How, Z. T.; Chelme-Ayala, P.; Benally, C.; Gamal El-Din, M. Z-scheme plasmonic Ag decorated Bi2WO6/NiO hybrids for enhanced photocatalytic treatment of naphthenic acids in real oil sands process water under simulated solar irradiation. J. Hazard. Mater. 2023, 454, 131441.
Jiang, W. C.; Deng, Y. H.; Su, R.; Xu, J. P.; Liu, L. High-detectivity and broadband MoS2 phototransistor array by coupling negative capacitance and local surface plasmon resonance effects. ACS Photonics 2024, 11, 2308–2315.
Wu, W. L.; Zhang, N.; Wang, Y. H. Construction of Au/ZnWO4/CdS ternary photocatalysts with oxygen vacancy modification for efficient photocatalytic hydrogen production. Adv. Funct. Mater. 2024, 34, 2316604.
Tsao, C. W.; Narra, S.; Kao, J. C.; Lin, Y. C.; Chen, C. Y.; Chin, Y. C.; Huang, Z. J.; Huang, W. H.; Huang, C. C.; Luo, C. W. et al. Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region. Nat. Commun. 2024, 15, 413.
Wang, W.; Deng, C. Y.; Xie, S. J.; Li, Y. F.; Zhang, W. Y.; Sheng, H.; Chen, C. C.; Zhao, J. C. Photocatalytic C–C coupling from carbon dioxide reduction on copper oxide with mixed-valence copper(I)/copper(II). J. Am. Chem. Soc. 2021, 143, 2984–2993.
Ren, L. T.; Yang, X. N.; Sun, X.; Wang, Y. L.; Li, H. Q.; Yuan, Y. P. Cascaded *CO–*COH intermediates on a nonmetallic plasmonic photocatalyst for CO2-to-C2H6 with 90.6% selectivity. Angew. Chem., Int. Ed. 2024, 63, e202404660.
Wang, J. Y.; Yang, C.; Mao, L.; Cai, X. Y.; Geng, Z. K.; Zhang, H. Y.; Zhang, J. Y.; Tan, X.; Ye, J. H.; Yu, T. Regulating the metallic Cu–Ga bond by S vacancy for improved photocatalytic CO2 reduction to C2H4. Adv. Funct. Mater. 2023, 33, 2213901.