Synergistic Pd species anchored in ordered macroporous In2O3 boosting solar-driven CO2 and H2O conversion

doi:10.1016/S1872-2067(25)64919-9

Abstract

Abstract:

Achieving efficient photocatalytic CO₂ reduction using H₂O as a hydrogen source requires the synergistic optimization of both charge and proton transfer between CO₂ reduction and H₂O oxidation half-reactions. However, conventional studies mostly focused on enhancing these half-reactions independently, overlooking the intrinsic interdependence between them. Herein, this work develops a photothermal catalyst (denoted as Pd_1+c/3DOM-In₂O₃) through engineering synergistic Pd single atoms (Pd₁) and Pd clusters (Pd_c) in three-dimensional ordered macroporous (3DOM) In₂O₃ framework. The mechanistic study reveals that the coexistence of Pd single atoms and clusters not only offers synergistic active sites to promote the reaction of CO₂ and H₂O, but also substantially improves the separation and transfer efficiencies of photogenerated electrons and holes. The Pd clusters facilitate H₂O dissociation to ensure an adequate supply of active hydrogen species as well as synergistically enhance the adsorption and activation of CO₂ at Pd single-atom sites. Furthermore, the enhanced photoabsorption in visible and near-infrared regions, attributed to the localized surface plasmon resonance of Pd clusters, leads to a significant increase in catalyst temperature under simulated solar irradiation. The integration of photocatalysis with the photothermal effect affords an intensified driving force for the selective conversion of CO₂ and H₂O into CO, thereby accelerating the reaction kinetics of the overall photocatalytic CO₂ reduction process. As a result, the Pd_1+c/3DOM-In₂O₃ catalyst exhibits excellent performance for solar-driven CO₂ reduction with H₂O vapor, achieving a remarkable CO production rate of 192.52 μmol g^-1 h^-1, which is 19.8-fold and 12.2-fold higher than those of pure 3DOM-In₂O₃ and Pd₁/3DOM-In₂O₃, respectively. This study provides valuable insights into the synergistic effect of metal single atoms and clusters toward both efficient photocatalysis and photothermal effect for solar-driven CO₂ reduction.

Key words: Photocatalytic CO₂ reduction, Photothermal effect, Pd species, Synergistic active sites, H₂O activation

Fuhao Yin, Qianyu Zhang, Mao Xu, Shupeng Wei, Yi Li, Pengzuo Chen, Yanying Zhao, Benxia Li. Synergistic Pd species anchored in ordered macroporous In₂O₃ boosting solar-driven CO₂ and H₂O conversion[J]. Chinese Journal of Catalysis, 2026, 82: 238-250.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64919-9

https://www.cjcatal.com/EN/Y2026/V82/I3/238

Figures/Tables 6

Scheme 1. Schematic illustration of the Pd1+c/3DOM-In2O3 photocatalyst for enhanced conversion of CO2 and H2O into CO.

Fig. 1. Synthesis and microstructure of the Pd1+c/3DOM-In2O3 catalyst. (a) Schematic diagram of the synthesis process. SEM image (b), TEM image (c), HRTEM image (d), and STEM images (e-h) with EDS element mapping images.

Fig. 2. Spectroscopic characterization of Pd1/3DOM-In2O3, Pd1+c/3DOM-In2O3 and Pdn/3DOM-In2O3 samples. XPS spectra of In 3d (a), O 1s (b), and Pd 3d (c). (d) CO-DRIFTS spectra. (e) Normalized Pd K-edge XANES spectra. (f) Fourier-transformed EXAFS spectra of k2-weighted Pd K-edge. (g-j) WT-EXAFS of k2-weighted Pd K-edge.

Fig. 3. Photocatalytic CO2 reduction performance. Evolution rates of products under different conditions: the Pd1+c/3DOM-In2O3(x) catalysts with different Pd/In molar ratios (x%) under UV-vis-NIR irradiation (a), di?erent photocatalysts under UV-vis-NIR irradiation (b), the optimal Pd1+c/3DOM-In2O3 catalyst under di?erent conditions (c), the optimal Pd1+c/3DOM-In2O3 catalyst under UV-vis-NIR irradiation at di?erent controlled temperatures (d), the optimal Pd1+c/3DOM-In2O3 catalyst under di?erent light irradiation and the surface temperature of the catalyst (e), and di?erent controlled conditions (f). (g) Mass spectrum of 13CO produced from 13CO2 photoreduction on the Pd1+c/3DOM-In2O3 catalyst. (h) Cycling test of the Pd1+c/3DOM-In2O3 catalyst in CO2 reduction reaction under UV-vis-NIR light.

Fig. 4. Investigations on H2O adsorption and activation. (a-d) Time-dependent DRIFTS spectra of H2O adsorption and activation on different catalysts. The fitted spectra (e) and peak area proportions (f) for three types of interfacial H2O adsorbed on different catalysts: (I) 3DOM-In2O3, (II) Pd1/3DOM-In2O3, (III) Pd1+c/3DOM-In2O3, and (IV) Pdn/3DOM-In2O3. (g) Fluorescence spectra for detecting ?OH radicals generated during photocatalytic CO2RR in the presence of 0.1 mmol L-1 coumarin. (h) Gibbs free energy profiles of H2O dissociation on different active sites.

Fig. 5. CO2 adsorption and reduction on the photocatalysts. (a) CO2 adsorption isotherms for different catalysts. (b) Apparent activation energy of the photocatalytic CO2RR with H2O on different catalysts. (c) In-situ DRIFTS spectrum during photocatalytic CO2RR on the Pd1+c/3DOM-In2O3 catalyst. (d) Gibbs free energy profiles for CO2 reduction at different sites of the catalysts. (e) Electron localization function of Pd1/3DOM-In2O3 and Pd1+c/3DOM-In2O3. (f) Proposed mechanism for photocatalytic conversion of CO2 and H2O to CO on the Pd1+c/3DOM-In2O3 catalyst.

References

[1]	Z. Jiang, X. Xu, Y. Ma, H. S. Cho, D. Ding, C. Wang, J. Wu, P. Oleynikov, M. Jia, J. Cheng, Y. Zhou, O. Terasaki, T. Peng, L. Zan, H. Deng, Nature, 2020, 586, 549-554.
[2]	S. Yoshino, T. Takayama, Y. Yamaguchi, A. Iwase, A. Kudo, Acc. Chem. Res., 2022, 55, 966-977.
[3]	W. Wang, W. Zhang, C. Deng, H. Sheng, J. Zhao, Angew. Chem. Int. Ed., 2024, 63, e202317969.
[4]	W. Zhao, W. Mo, Y. Zhang, L. Hu, Y. Zheng, Z. Chen, X. Niu, Y. Zhao, L. Liu, S. Zhong, S. Bai, Nano Res., 2024, 17, 5022-5030.
[5]	M. Lin, M. Luo, Y. Liu, J. Shen, J. Long, Z. Zhang, Chin. J. Catal., 2023, 50, 239-248.
[6]	C. Yang, Q. Zhang, W. Wang, B. Cheng, J. Yu, S. Cao, Sci. China Mater., 2024, 67, 1830-1838.
[7]	Q. Xu, J. Han, F. Tian, X. Zhao, J. Rong, J. Zhang, P. She, J.-S. Qin, H. Rao, J. Am. Chem. Soc., 2025, 147, 10587-10597.
[8]	L. Hu, Y. Zhang, Q. Lin, F. Cao, W. Mo, S. Zhong, H. Lin, L. Xie, L. Zhao, S. Bai, Chin. J. Catal., 2025, 68, 311-325.
[9]	M. Li, S. Wu, D. Liu, Z. Ye, L. Wang, M. Kan, Z. Ye, M. Khan, J. Zhang, J. Am. Chem. Soc., 2024, 146, 15538-15548.
[10]	K. Yan, L. Chen, Y. Hu, T. Wang, C. Chen, C. Gao, Y. Huang, B. Li, Nano Res., 2024, 17, 1056-1065.
[11]	Y. Ren, Y. Fu, N. Li, C. You, J. Huang, K. Huang, Z. Sun, J. Zhou, Y. Si, Y. Zhu, W. Chen, L. Duan, M. Liu, Nat. Commun., 2024, 15, 4675.
[12]	Y. Ren, Y. Si, M. Du, C. You, C. Zhang, Y.-H. Zhu, Z. Sun, K. Huang, M. Liu, L. Duan, N. Li, Angew. Chem. Int. Ed., 2024, 63, e202410474.
[13]	M. Liang, X. Shao, J. Y. Choi, Y. D. Kim, T. T. Tran, J. Kim, Y. Hwang, M. G. Kim, Y. Cho, S. Akhtar, H. Lee, J. Energy Chem., 2024, 98, 714-720.
[14]	Z. Wei, M. Wang, X. Lu, Z. Zhou, Z. Tang, C. Chang, Y. Yang, S. Li, P. Gao, Chin. J. Catal., 2025, 72, 301-313.
[15]	Q.-J. Xu, J.-W. Jiang, X.-F. Wang, L.-Y. Duan, H. Guo, Rare Met., 2023, 42, 1888-1898.
[16]	X. Wan, Y. Zhao, Y. Li, J. Ma, Y. Gu, C. Liu, Y. Luo, G. Yang, Y. Cui, D. Liu, Y. Xiong, Angew. Chem. Int. Ed., 2025, 64, e202505244.
[17]	X. Wang, Q. Li, Q. Lin, R. Zhang, M. Ding, J. Mater. Sci. Technol., 2022, 111, 204-210.
[18]	Z. Jiang, Q. Long, B. Cheng, R. He, L. Wang, J. Mater. Sci. Technol., 2023, 162, 1-10.
[19]	W. Lyu, Y. Liu, J. Zhou, D. Chen, X. Zhao, R. Fang, F. Wang, Y. Li, Angew. Chem. Int. Ed., 2023, 62, e202310733.
[20]	Z. Chen, S. Wu, J. Ma, S. Mine, T. Toyao, M. Matsuoka, L. Wang, J. Zhang, Angew. Chem. Int. Ed., 2021, 60, 11901-11909.
[21]	K. Zhu, C. Fang, M. Pu, J. Song, D. Wang, X. Zhou, J. Mater. Sci. Technol., 2023, 141, 78-99.
[22]	J. Li, Y. Li, X. Wang, Z. Yang, G. Zhang, Chin. J. Catal., 2023, 51, 145-156.
[23]	Z. Ma, Q. Wang, L. Liu, R.-A. Zhang, Q. Liu, P. Liu, L. Wu, C. Liu, Y. Bai, Y. Zhang, H. Pan, X. Zheng, Nano Res., 2024, 17, 3745-3751.
[24]	H. Fu, J. Tian, Q. Zhang, Z. Zheng, H. Cheng, Y. Liu, B. Huang, P. Wang, Chin. J. Catal., 2024, 64, 143-151.
[25]	Y. Shen, C. Ren, L. Zheng, X. Xu, R. Long, W. Zhang, Y. Yang, Y. Zhang, Y. Yao, H. Chi, J. Wang, Q. Shen, Y. Xiong, Z. Zou, Y. Zhou, Nat. Commun., 2023, 14, 1117.
[26]	H. He, Y. Ren, S. Lan, H. Zhang, Y.-H. Zhu, R. Peng, J. Zhou, M. Liu, Y. Si, D. Jing, N. Li, Appl. Catal. B, 2025, 378, 125623.
[27]	T. Pu, J. Ding, F. Zhang, K. Wang, N. Cao, E. J. M. Hensen, P. Xie, Angew. Chem. Int. Ed., 2023, 62, e202305964.
[28]	L. Cheng, B. Li, H. Yin, J. Fan, Q. Xiang, J. Mater. Sci. Technol., 2022, 118, 54-63.
[29]	E. H. Kim, M. H. Lee, J. Kim, E. C. Ra, J. H. Lee, J. S. Lee, Chin. J. Catal., 2023, 47, 214-221.
[30]	Q. Li, P. Zhang, H. Li, Y. Wang, D. Tang, Q. Li, J. Wu, Sci. China Mater., 2024, 67, 3197-3205.
[31]	J. Chen, Y. Ren, Y. Fu, Y. Si, J. Huang, J. Zhou, M. Liu, L. Duan, N. Li, ACS Nano, 2024, 18, 13035-13048.
[32]	L. Zhang, S. Hussain, Q. Li, J. Yang, J. Energy Chem., 2024, 91, 254-265.
[33]	Q. Li, Q. Tang, P. Xiong, D. Chen, J. Chen, Z. Wu, H. Wang, Chin. J. Catal., 2023, 46, 177-190.
[34]	L. Li, X. Dai, M. Lu, C. Guo, S. M. Wabaidur, X.-L. Wu, Z. Lou, Y. Zhong, Y. Hu, Adv. Powder Mater., 2024, 3, 100170.
[35]	P. Liu, Z. Huang, X. Gao, X. Hong, J. Zhu, G. Wang, Y. Wu, J. Zeng, X. Zheng, Adv. Mater., 2022, 34, 2200057.
[36]	Y. Duan, H. Zhao, J. Ji, Z. Shen, Y. Wang, Y. Du, Nano Lett., 2025, 25, 6227-6234.
[37]	J. Fang, C. Zhu, L. Fang, Y. Chen, H. Hu, Y. Wu, Q. Chen, J. Mao, Sci. China Mater., 2024, 67, 2949-2956.
[38]	T. Dong, X. Wu, F. Xiao, J. Ji, P. Huang, H. Huang, ACS Catal., 2025, 15, 5103-5112.
[39]	M. Ren, J. Meng, Y. Yang, X. Zhang, G. Yang, L. Qin, Y. Guo, Appl. Catal. B, 2024, 345, 123680.
[40]	C. Hu, X. Chen, J. Low, Y.-W. Yang, H. Li, D. Wu, S. Chen, J. Jin, H. Li, H. Ju, C.-H. Wang, Z. Lu, R. Long, L. Song, Y. Xiong, Nat. Commun., 2023, 14, 221.
[41]	M. Wang, J. Jia, Z. Meng, J. Xia, X. Hu, F. Xue, H. Peng, X. Meng, J. Yi, X. Chen, J. Li, Y. Guo, Y. Xu, X. Huang, Sci. Adv., 2024, 10, eado9664.
[42]	X. Zhang, R. Shi, Z. Li, J. Zhao, H. Huang, C. Zhou, T. Zhang, Adv. Energy Mater., 2022, 12, 2103740.
[43]	H. He, Y. Ren, Y.-H. Zhu, R. Peng, S. Lan, J. Zhou, B. Yang, Y. Si, N. Li, ACS Catal., 2025, 15, 10480-10520.
[44]	X. Tao, R. Long, D. Wu, Y. Hu, G. Qiu, Z. Qi, B. Li, R. Jiang, Y. Xiong, Small, 2020, 16, 2001782.
[45]	B. Chen, J. Yu, R. Wang, X. Zhang, B. He, J. Jin, H. Wang, Y. Gong, Sci. China Mater., 2022, 65, 139-146.
[46]	K. Zhang, H. Chen, W. Pei, H. Dai, J. Li, Y. Zhu, Nano Res., 2023, 16, 8871-8881.
[47]	J. Li, B. Sheng, Y. Chen, J. Yang, P. Wang, Y. Li, T. Yu, H. Pan, L. Qiu, Y. Li, J. Song, L. Zhu, X. Wang, Z. Huang, B. Zhou, Nat. Commun., 2024, 15, 7393.
[48]	Y. Wang, J. Ren, Q. Guo, K. Ma, W. Guo, F. Cao, S. Zhang, Nano Res., 2025, 18, 94907553.
[49]	J. C. C. Fan, J. B. Goodenough, J. Appl. Phys., 1977, 48, 3524-3531.
[50]	M. Xu, F. Liu, S. Liu, J. Ma, M. Yao, X. Wang, J. Cao, J. Mater. Sci. Technol., 2025, 221, 289-301.
[51]	H. Li, X. Sun, T. Li, Z. Zhao, H. Wang, X. Yang, C. Zhang, F. Wang, Nat. Commun., 2024, 15, 10176.
[52]	C. Tang, S. Du, H. Huang, S. Tan, J. Zhao, H. Zhang, W. Ni, X. Yue, Z. Ding, Z. Zhang, R. Yuan, W. Dai, X. Fu, M. B. J. Roeffaers, J. Long, ACS Catal., 2023, 13, 6683-6689.
[53]	Y. Guo, Y. Li, X. Du, L. Li, Q. Jiang, B. Qiao, Nano Res., 2022, 15, 10037-10043.
[54]	H. Tiznado, S. Fuentes, F. Zaera, Langmuir, 2004, 20, 10490-10497.
[55]	L.-F. Shen, B.-A. Lu, Y.-Y. Li, J. Liu, Z.-C. Huang-fu, H. Peng, J.-Y. Ye, X.-M. Qu, J.-M. Zhang, G. Li, W.-B. Cai, Y.-X. Jiang, S.-G. Sun, Angew. Chem. Int. Ed., 2020, 59, 22397-22402.
[56]	Y. Wang, J. Zhang, J. Zhao, Y. Wei, S. Chen, H. Zhao, Y. Su, S. Ding, C. Xiao, ACS Catal., 2024, 14, 3457-3465.
[57]	C. Chen, L. Chen, Y. Hu, K. Yan, T. Wang, Y. Huang, C. Gao, J. Mao, S. Liu, B. Li, J. Energy Chem., 2023, 86, 599-608.
[58]	C. Shen, X.-Y. Meng, R. Zou, K. Sun, Q. Wu, Y.-X. Pan, C.-J. Liu, Angew. Chem. Int. Ed., 2024, 63, e202402369.
[59]	F. Raziq, C. Feng, M. Hu, S. Zuo, M. Z. Rahman, Y. Yan, Q.-H. Li, J. Gascon, H. Zhang, J. Am. Chem. Soc., 2024, 146, 21008-21016.
[60]	X. Wang, B. Hu, Y. Li, Z. Yang, G. Zhang, Chin. J. Catal., 2024, 66, 257-267.
[61]	J. Wang, H. Zhang, Y. Nian, Y. Chen, H. Cheng, C. Yang, Y. Han, X. Tan, J. Ye, T. Yu, Adv. Funct. Mater., 2024, 34, 2406549.
[62]	S. Xia, X. Yin, Y. Chen, L. Zhang, J. Yu, B. Ding, J. Yan, ACS Nano, 2025, 19, 1519-1529.
[63]	R. Li, P. Feng, B. Li, J. Zhu, Y. Zhang, Z. Zhang, J. Zhang, Y. Ding, Chin. J. Catal., 2025, 73, 242-251.
[64]	X. Li, J. Liu, J. Wu, L. Zhang, D. Cao, D. Cheng, ACS Catal., 2024, 14, 2369-2379.
[65]	Z.-X. Sun, C. Zhou, Z. Chen, Y. Zeng, T. Sun, X. Dong, L. Yang, X. Wang, Q. Wu, H. Huang, L. He, Z. Hu, Angew. Chem. Int. Ed., 2025, 64, e202508090.

Synergistic Pd species anchored in ordered macroporous In₂O₃ boosting solar-driven CO₂ and H₂O conversion

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