Asymmetric oxygen-bridged Bi-In dual sites for efficient photothermal CO2 methanation

doi:10.1016/S1872-2067(25)64922-9

Abstract

Abstract:

Photothermal coupling catalytic CO₂/H₂O to CH₄ is recognized as an effective strategy for addressing environmental concerns and energy crisis. However, hydrogen evolution reaction (HER) competition and weak intermediate adsorption limiting CH₄ selectivity and yield during the reaction process. Herein, we incorporate Bi into the In₂O₃ lattice to create an oxygen-bridged asymmetric bimetallic In-O-Bi (In-O-Bi bridge) sites. The optimized Bi/In₂O₃ catalyst achieves CH₄ yield of 214.1 μmol·g^-1 with 96.7% selectivity. The exceptional catalytic activity of Bi/In₂O₃stems from two key synergistic effects: (1) the cooperative interaction between Bi and In as p-block metals effectively suppress the competing HER, and (2) the unique In-O-Bi bridge configuration induces significant electron delocalization through p-orbital hybridization. This electronic modulation creates highly active catalytic centers, with In sites preferentially facilitating H₂O dissociation while Bi sites selectively promote CO₂ reduction. Moreover, the electron delocalization effect in the In-O-Bi bridge sites enhances the adsorption and electron transfer capabilities of the Bi/In₂O₃ surface for key CHO species, and reduces the energy barrier, thereby enabling efficient CH₄ production. These findings provide crucial insights into the design of photothermal catalysts, highlighting the transformative potential of oxygen-bridged asymmetric bimetallic units in efficient CO₂ methanation and sustainable energy technologies.

Key words: Photothermal catalysis, CO₂ methanation, Orbital hybridization, Electron delocalization, In-O-Bi bridge sites

Mang Zheng, Qi Li, Qianxi Liu, Huiquan Gu, Mingyang Liu, Qi Liu, Baojiang Jiang. Asymmetric oxygen-bridged Bi-In dual sites for efficient photothermal CO₂ methanation[J]. Chinese Journal of Catalysis, 2026, 83: 351-362.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64922-9

https://www.cjcatal.com/EN/Y2026/V83/I4/351

Figures/Tables 5

Fig. 1. (a) Schematic representation of the synthesis of Bi/In2O3. (b) Rietveld refinement of the XRD pattern structure of Bi/In2O3. (c) SEM. (d) TEM. (e) A high-resolution TEM. (f) HADDF-STEM and corresponding elemental mapping images of Bi/In2O3.

Fig. 2. In 3d (a) and Bi 4f (b) XPS spectra. (c) Normalized Bi L3-edge XANES spectra with Bi2O3 and Bi foil references. (d) Average Bi valence state in Bi/In2O3. (e) k2-weighted Bi L3-edge Fourier transform EXAFS spectra with references. (f) Bi L-edge EXAFS data (line) and best fits (circles) for Bi/In2O3 in k2-weighted r-space. (g-i) wavelet-transform EXAFS images of Bi/In2O3, Bi2O3, and Bi foil.

Fig. 3. (a) Temporal evolution of CO2 reduction products over In2O3 and Bi/In2O3. (b) Activation energies of catalysts under photothermal conditions. (c) Product distribution for Bi/In2O3 series. (d) Electron participation and O2 evolution comparison during methanation. (e) The cycling tests of Bi/In2O3 sample. The aforementioned experiments were conducted at 300 °C with 1.77 W·cm-2. (f) Product distribution under various conditions (10 h). (g) Under constant reaction temperature (573 K), the trend of product variation with light intensity. (h) Activation energies of Bi/In2O3 under photothermal catalysis and Thermal catalysis conditions. (i) Under constant light intensity (1.77 W·cm-2), the trend of product variation with temperature. Data are presented as the mean ± standard deviation from three independent experiments, significance was defined as p≤0.05.

Fig. 4. (a) Photothermal CO2 methanation reaction under various conditions. (b) GC-MS spectrum of the products in photothermal 13CO2 and D2O methanation reaction. (c,d) CO2-TPD and H2O-TPD spectra of In2O3 and Bi/In2O3. In-situ DRIFTS of spectra of In2O3 (e) and Bi/In2O3 (f) during H2O and CO2 adsorption. In-situ DRIFTS spectra of In2O3 (g) and Bi/In2O3 (h) under visible light and 300 °C after adsorption saturation. (The “ads” represents surface adsorbed states.)

Fig. 5. (a,b) The projected density of states (PDOS) of Bi/In2O3 and In2O3 model in *CO2 states. (c) Free energy profile for the HER process on Bi/In2O3 and In2O3 model. (d) PDOS of Bi/In2O3 and In2O3 model after *H adsorption. (e,f) Electronic location function results. (g) Energy barrier for H2O dissociation on the In and Bi sites of Bi/In2O3. (h,i) Charge density difference of CHO species on In2O3 and Bi/In2O3 model. Yellow and blue represent electron accumulation and depletion, respectively. (j) Illustration of the mechanism of photocatalytic CO2 reduction and H2O oxidation on Bi/In2O3.

References

[1]	M. Bonchio, J. Bonin, O. Ishitani, T.-B. Lu, T. Morikawa, A. J. Morris, E. Reisner, D. Sarkar, F. M. Toma, M. Robert, Nat. Catal., 2023, 6, 657-665.
[2]	U. Ulmer, T. Dingle, P. N. Duchesne, R. H. Morris, A. Tavasoli, T. Wood, G. A. Ozin, Nat. Commun., 2019, 10, 3169.
[3]	Y. Li, Z. Liu, Z. Rao, F. Yu, W. Bao, Y. Tang, H. Zhao, J. Zhang, Z. Wang, J. Li, Z. Huang, Y. Zhou, Y. Li, B. Dai, Appl. Catal. B, 2022, 319, 121903.
[4]	P. Wang, F. Yang, J. Qu, Y. Cai, X. Yang, C.-M. Li, J. Hu, Small, 2024, 20, 2400700.
[5]	S. Xie, Q. Zhang, G. Liu, Y. Wang, Chem. Commun., 2016, 52, 35-59.
[6]	X. Li, J. Wen, J. Low, Y. Fang, J. Yu, Sci. China Mater., 2014, 57, 70-100.
[7]	Z.-J. Wang, H. Song, H. Liu, J. Ye, Angew. Chem. Int. Ed., 2020, 59, 8016-8035.
[8]	S. Fang, Y.-H. Hu, Chem. Soc. Rev., 2022, 51, 3609-3647.
[9]	J. Fu, K. Jiang, X. Qiu, J. Yu, M. Liu, Mater. Today, 2020, 32, 222-243.
[10]	R. Ye, J. Ding, T. R. Reina, M. S. Duyar, H. Li, W. Luo, R. Zhang, M. Fan, G. Feng, J. Sun, J. Liu, Nat. Synth, 2025, 4, 288-302.
[11]	A. T. Landers, M. Fields, D. A. Torelli, J. Xiao, T. R. Hellstern, S. A. Francis, C. Tsai, J. Kibsgaard, N. S. Lewis, K. Chan, C. Hahn, T. F. Jaramillo, ACS Energy Lett., 2018, 3, 1450-1457.
[12]	J. Li, T. Xiang, X. Liu, M. N. Ghazzal, Z.-Q. Liu, Angew. Chem. Int. Ed., 2024, 63, e202407287.
[13]	L. Li, C. Tang, B. Xia, H. Jin, Y. Zheng, S.-Z. Qiao, ACS Catal., 2019, 9, 2902-2908.
[14]	J. Meng, K. Wang, Y. Wang, J. Ma, C. Ban, Y. Feng, B. Zhang, K. Zhou, L. Gan, G. Han, D. Yu, X. Zhou, Nano Res., 2024, 17, 1190-1198.
[15]	Z. Cai, J. Dai, W. Li, K. B. Tan, Z. Huang, G. Zhan, J. Huang, Q. Li, ACS Catal., 2020, 10, 13275-13289.
[16]	D. Friedmann, R. A. Caruso, Sol. RRL, 2021, 5, 2100086.
[17]	O. Bierwagen, Semicond. Sci. Technol., 2015, 30, 024001.
[18]	C. Liang, H. Ai, L. Lin, X. Lu, L. Li, H. Zhang, P. Wang, Z. Zheng, Z. Wang, H. Cheng, Y. Dai, D. Xing, B. Huang, Y. Liu, Small, 2025, 21, 2500744.
[19]	M. Huang, L. Song, N. Wang, Y. Fu, R. Ren, Z. Li, Y. Lu, J. Xu, Q. Liu, Angew. Chem. Int. Ed., 2025, 64, e202414893.
[20]	Y. Zheng, Q. Zhao, W. Xu, R. Han, Q. Liu, ACS Sustainable Chem. Eng., 2025, 13, 3567-3576.
[21]	C. Wang, X. Wu, H. Sun, Z. Xu, C. Xu, X. Wang, M. Li, Y. Wang, Y. Tang, J. Jiang, K. Sun, G. Fu, Energy Environ. Sci., 2025, 18, 4276-4287.
[22]	L. Zhang, S. Chen, T. Du, X. Zhao, A. Dong, L. Zhang, T. Li, L. Li, C. Yan, T. Qian, ACS Nano, 2024, 18, 34195-34206.
[23]	F. Nekouei, C. J. Pollock, T. Wang, Z. Zheng, Y. Zhang, Z. Fusco, H. Jin, T. R. Ramireddy, A. A. Wibowo, T. Lu, S. Nekouei, F. Keshtpour, J. Langley, E. H. Abdelkader, N. Cox, Z. Yin, H. Nguyen, A. Glushenkov, S. Karuturi, Z. Liu, L. Wei, H. Li, Y. Liu, ACS Catal., 2025, 15, 1431-1443.
[24]	T. Yan, N. Li, L. Wang, W. Ran, P. N. Duchesne, L. Wan, N. T. Nguyen, L. Wang, M. Xia, G. A. Ozin, Nat. Commun., 2020, 11, 6095.
[25]	Y. Dong, K. K. Ghuman, R. Popescu, P. N. Duchesne, W. Zhou, J. Y. Y. Loh, F. M. Ali, J. Jia, D. Wang, X. Mu, C. Kübel, L. Wang, L. He, M. Ghoussoub, Q. Wang, T. E. Wood, L. M. Reyes, P. Zhang, N. P. Kherani, C. V. Singh, G. A. Ozin, Adv. Sci., 2018, 5, 1700732.
[26]	Z. Wang, Y. Zhang, J. Zhang, N. Xu, T. Lu, B. Zhuang, G. Liu, W. Yang, H. Lei, B. Tian, J. Qiao, Chin. J. Catal., 2025, 73, 311-321.
[27]	J. Zhu, J. Li, R. Lu, R. Yu, S. Zhao, C. Li, L. Lv, L. Xia, X. Chen, W. Cai, J. Meng, W. Zhang, X. Pan, X. Hong, Y. Dai, Y. Mao, J. Li, L. Zhou, G. He, Q. Pang, Y. Zhao, C. Xia, Z. Wang, L. Dai, L. Mai, Nat. Commun., 2023, 14, 4670.
[28]	M. Huang, J. Ge, H. Tan, X. Ji, Y. Liang, B. Xi, W. Zhou, S. Xiong, Adv. Energy Mater., 2025, 15, 2402780.
[29]	X. Li, B. Kang, F. Dong, Z. Zhang, X. Luo, L. Han, J. Huang, Z. Feng, Z. Chen, J. Xu, B. Peng, Z.-L. Wang, Nano Energy, 2021, 81, 105671.
[30]	L. Zhang, J. Ran, S.-Z. Qiao, M. Jaroniec, Chem. Soc. Rev., 2019, 48, 5184-5206.
[31]	Q. Li, X. Li, M. Zheng, F. Luo, L. Zhang, B. Zhang, B. Jiang, Adv. Funct. Mater., 2025, 35, 2417279.
[32]	J. Zhai, Z. Xia, B. Zhou, H. Wu, T. Xue, X. Chen, J. Jiao, S. Jia, M. He, B. Han, Nat. Commun., 2024, 15, 1109.
[33]	Z. Luo, F. Yang, S. Zhang, G. He, C. Du, L. Zhang, Z. Duan, J. Huang, Y.-K. Peng, D. Mei, Y. Wang, H. Xiong, Appl. Catal. B, 2025, 375, 125397.
[34]	K. Zheng, S. Liu, J. Zhu, Z. Dai, C. Liu, B. Li, Y. Zheng, X. Chen, L. Zhai, Y. Wu, W. Liu, M. Fan, J. Hu, Y. Pan, J. Zhu, F. Sun, Y. Sun, Y. Xie, Angew. Chem. Int. Ed., 2025, 64, e202508259.
[35]	M. Xu, B. Chang, J. Li, H. Wang, P. Huo, Chin. J. Catal., 2025, 71, 114-127.
[36]	M. Smyrnioti, C. Tampaxis, T. Steriotis, T. Ioannides, Catal. Today, 2020, 357, 495-502.
[37]	X. Zhang, F. Bi, Z. Zhu, Y. Yang, S. Zhao, J. Chen, X. Lv, Y. Wang, J. Xu, N. Liu, Appl. Catal. B, 2021, 297, 120393.
[38]	Q. Li, H. Wang, M. Zhang, G. Li, J. Chen, H. Jia, Angew. Chem. Int. Ed., 2023, 62, e202300129.
[39]	J. Zhou, J. Li, L. Kan, L. Zhang, Q. Huang, Y. Yan, Y. Chen, J. Liu, S.-L. Li, Y.-Q. Lan, Nat. Commun., 2022, 13, 4681.
[40]	W. Bi, Y. Hu, H. Jiang, L. Zhang, C. Li, Adv. Funct. Mater., 2021, 31, 2010780.
[41]	W. Shangguan, Q. Liu, Y. Wang, N. Sun, Y. Liu, R. Zhao, Y. Li, C. Wang, J. Zhao, Nat. Commun., 2022, 13, 3894.
[42]	H. Guan, Y. Liu, X. Hu, J. Wu, T.-N. Ye, Y. Lu, H. Hosono, Q. Li, F. Pan, Angew. Chem. Int. Ed., 2024, 63, e202400119.
[43]	S. Yin, Y. Zhou, Z. Liu, H. Wang, X. Zhao, Z. Zhu, Y. Yan, P. Huo, Nat. Commun., 2024, 15, 437.
[44]	X. Li, H. Lin, X. Jia, S. Chen, J. Cao, Chin. J. Catal., 2025, 73, 205-221.
[45]	J. Li, Nano-Micro Lett., 2022, 14, 112.
[46]	J. Li, R. Wang, L. Han, T. Wang, Y. Asakura, C. Wang, G. Wang, X. Xu, Y. Yamauchi, Nat. Commun., 2025, 16, 1996.
[47]	Y. He, S. Dai, J. Sheng, Q. Ren, Y. Lv, Y. Sun, F. Dong, Proc. Natl. Acad. Sci. U. S. A., 2024, 121, e2322107121.
[48]	M. Li, W. Luo, A. Züttel, J. Catal., 2021, 395, 315-324.
[49]	H. F. Shakir, T. Zhao, M. U. Farooq, A. Jalil, J. Mater. Sci. Technol., 2025, 224, 183-190.
[50]	H. Zhao, Y. Xie, B. Lv, G. Jing, Y. Li, Appl. Catal. B Environ. Energy, 2025, 371, 125234.

Asymmetric oxygen-bridged Bi-In dual sites for efficient photothermal CO₂ methanation

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