CO2-free hydrogen production from solar-driven photothermal catalytic decomposition of methane

doi:10.1016/S1872-2067(25)64703-6

Abstract

Abstract:

CO₂-free H₂ refers to H₂ production process without CO₂ emission, which is a promising clean energy in the future. Catalytic decomposition of methane (CDM) is a competitive technology to produce CO₂-free H₂ with large-scale. However, CDM reaction is highly endothermic and is kinetically and thermodynamically unfavorable, which typically requires a harsh reaction temperature above 800 °C. In this work, solar-driven photothermal catalytic decomposition of methane was firstly introduced to produce CO₂-free H₂ relying solely on solar energy as the driving force. A high H₂ yield of 204.6 mmol g^-1 h^-1 was observed over Ni-CeO₂ interface under photothermal conditions, along with above 87% reduction in the apparent activation energy (11.2 vs. 87.3 kJ mol^-1) when comparing with the traditional thermal catalysis. Further studies suggested that Ni/CeO₂ catalyst enhanced optical absorption in visible-infrared region to ensure the heat energy for methane decomposition. The generated electrons and holes participated in the redox process of photo-driven CDM reaction with enhanced separation ability of hot carriers excited by ultraviolet-visible light, which lowered activation energy and improved the photothermal catalytic activity. This work provides a promising photothermal catalytic strategy to produce CO₂-free H₂ under mild conditions.

Key words: CO₂-free hydrogen, Hydrogen production, Photothermal catalysis, Methane decomposition, Methane conversion

Yihan Zheng, Yuxin Wang, Ruitao Li, Haoran Yang, Yuanyuan Dai, Qiang Niu, Tiejun Lin, Kun Gong, Liangshu Zhong. CO₂-free hydrogen production from solar-driven photothermal catalytic decomposition of methane[J]. Chinese Journal of Catalysis, 2025, 73: 289-299.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64703-6

https://www.cjcatal.com/EN/Y2025/V73/I6/289

Figures/Tables 7

Fig. 1. Schematic illustration of various routes for hydrogen production.

Fig. 2. Hydrogen yield of various CeO2-based catalysts (a), various Ni/CeO2 catalysts with different Ni contents (b), comparison between photothermal and thermal reactions (c) and Ni/CeO2 under various light regions (d). Apparent activation energy comparison between photothermal and thermal reaction (e) and the comparison of photothermal catalysis over Ni/CeO2 with previous works for CDM reaction (f). Reaction conditions: a continuous flow of CH4/N2 = 9/1 at 10 mL min-1, 5.28 W cm-2 irradiation intensity. The using evaluation data was the average performance for 2 h reaction.

Fig. 3. XRD patterns of various samples at 2θ of 25°-90° (a) and 25°-35° (b). (c) Fourier-transform of the k3-weighted EXAFS spectra for Ni k-edge. TEM images of CeO2 (d), Ni (e), and Ni/CeO2 (f). (g) HRTEM image of Ni/CeO2. (h) TEM images and the corresponding elemental mapping for Ce, Ni and O of Ni/CeO2.

Fig. 4. H2-TPR (a) and Raman spectra (b) for various samples. XPS Ce 3d (c) and O 1s (d) spectra.

Fig. 5. UV-vis-IR diffuse-reflectance (a), transient photocurrent responses (b), PL (c), EIS plot (d), and TRPL (e) of CeO2, Ni and Ni/CeO2 catalysts. (f) TGA curves of various spent catalysts.

Fig. 6. (a) MS signal of hydrogen in CH4-TPSR for various samples. EPR spectra identifying ·CH3 of various samples (b), comparison of different conditions (c) and adding trapping agents (d).

Fig. 7. In-situ DRIFTS of CH4 adsorption under dark conditions (a) and the corresponding specific regions of 3200-2800 cm-1 (b) and 1500-1200 cm-1 (c). In-situ DRIFTS of CH4 adsorption under light conditions (d) and the corresponding specific regions of 3200-2800 cm-1 (e) and 1500-1200 cm-1 (f). The ratio of the peak intensities of the methyl group at 1470 cm-1 (g) and 1386 cm-1 (h) to the peak intensity of methane. Reaction conditions: a continuous flow of 2 mL min-1 CH4 and 18 mL min-1 Ar under 300 °C with or without irradiation.

References

[1]	J. F. Dean, Science, 2020, 367, 846-848.
[2]	U. P. M. Ashik, W. M. A. Wan Daud, H. F. Abbas, Renewable Sustainable Energy Rev., 2015, 44, 221-256.
[3]	H. Dotan, A. Landman, S. W. Sheehan, K. D. Malviya, G. E. Shter, D. A. Grave, Z. Arzi, N. Yehudai, M. Halabi, N. Gal, N. Hadari, C. Cohen, A. Rothschild, G. S. Grader, Nat. Energy, 2019, 4, 786-795.
[4]	S. Stephens-Romero, M. Carreras-Sospedra, J. Brouwer, D. Dabdub, S. Samuelsen, Environ. Sci. Technol., 2009, 43, 9022-9029.
[5]	C. Tarhan, M. Ali Çil, J. Energy Storage, 2021, 40, 102676.
[6]	M. Ishaq, I. Dincer, Renewable Energy, 2024, 237, 121642.
[7]	M. G. Rasul, M. A. Hazrat, M. A. Sattar, M. I. Jahirul, M. J. Shearer, Energy Convers. Manag., 2022, 272, 116326.
[8]	D. Çelik, M. Yıldız, Int. J. Hydrogen Energy, 2017, 42, 23395-23401.
[9]	M. Khalil, I. Dincer, J. Cleaner Prod., 2024, 440, 140895.
[10]	Global Hydrogen Review 2024-Analysis https://www.iea.org/reports/global-hydrogen-review-2024 (accessed Dec 17, 2024).
[11]	S. T. Wismann, J. S. Engbæk, S. B. Vendelbo, F. B. Bendixen, W. L. Eriksen, K. Aasberg-Petersen, C. Frandsen, I. Chorkendorff, P. M. Mortensen, Science, 2019, 364, 756-759.
[12]	L. Barreto, A. Makihira, K. Riahi, Int. J. Hydrogen Energy, 2003, 28, 267-284.
[13]	W. N. Manan, W. N. R. Wan Isahak, Z. Yaakob, Catalysts, 2022, 12, 452.
[14]	L. Barelli, G. Bidini, F. Gallorini, S. Servili, Energy, 2008, 33, 554-570.
[15]	Y. Cho, A. Yamaguchi, M. Miyauchi, Catalysts, 2021, 11, 18.
[16]	S. Wang, S. A. Nabavi, P. T. Clough, Int. J. Hydrogen Energy, 2023, 48, 15879-15893.
[17]	W. Yan, S. K. Hoekman, Environ. Prog. Sustain. Energy, 2014, 33, 213-219.
[18]	P. Perreault, C.-R. Boruntea, H. Dhawan Yadav, I. Portela Soliño, N. B. Kummamuru, Energies, 2023, 16, 7316.
[19]	L. Zhou, D. F. Swearer, C. Zhang, H. Robatjazi, H. Zhao, L. Henderson, L. Dong, P. Christopher, E. A. Carter, P. Nordlander, N. J. Halas, Science, 2018, 362, 69-72.
[20]	S. Sakthivel, Energy Fuels, 2024, 38, 20033-20056.
[21]	Z. Li, X. Liu, Q. Yu, X. Qu, J. Wan, Z. Xiao, J. Chi, L. Wang, Chin. J. Catal., 2024, 63, 33-60.
[22]	C. Lang, Y. Xu, X. Yao, Chin. J. Catal., 2024, 64, 4-31.
[23]	J. Rissman, C. Bataille, E. Masanet, N. Aden, W. R. Morrow III, N. Zhou, N. Elliott, R. Dell, N. Heeren, B. Huckestein, J. Cresko, S. A. Miller, J. Roy, P. Fennell, B. Cremmins, T. Koch Blank, D. Hone, E. D. Williams, S. de la Rue du Can, B. Sisson, M. Williams, J. Katzenberger, D. Burtraw, G. Sethi, H. Ping, D. Danielson, H. Lu, T. Lorber, J. Dinkel, J. Helseth, Appl. Energy, 2020, 266, 114848.
[24]	W. Fang, J. Yan, Z. Wei, J. Liu, W. Guo, Z. Jiang, W. Shangguan, Chin. J. Catal., 2024, 60, 1-24.
[25]	W.-K. Chong, B.-J. Ng, L.-L. Tan, S.-P. Chai, Chem. Soc. Rev., 2024, 53, 10080-10146.
[26]	N. Xiao, S. Li, X. Li, L. Ge, Y. Gao, N. Li, Chin. J. Catal., 2020, 41, 642-671.
[27]	M. Pudukudy, Z. Yaakob, Q. Jia, M. Sobri Takriff, New J. Chem., 2018, 42, 14843-14856.
[28]	D. Ayillath Kutteri, I.-W. Wang, A. Samanta, L. Li, J. Hu, Catal. Sci. Technol., 2018, 8, 858-869.
[29]	D. Wang, J. Zhang, J. Sun, W. Gao, Y. Cui, Int. J. Hydrogen Energy, 2019, 44, 7205-7215.
[30]	H. Sun, S. Ren, X. Ji, W. Song, Q. Guo, B. Shen, Int. J. Hydrogen Energy, 2023, 48, 13081-13096.
[31]	J.-M. Oh, C. C. Venters, C. Di, A. M. Pinto, L. Wan, I. Younis, Z. Cai, C. Arai, B. R. So, J. Duan, G. Dreyfuss, Nat. Commun., 2020, 11, 1.
[32]	M. Pudukudy, Z. Yaakob, Q. Jia, M. S. Takriff, Appl. Surf. Sci., 2019, 467-468, 236-248.
[33]	L. Chen, Z. Song, S. Zhang, C.-K. Chang, Y.-C. Chuang, X. Peng, C. Dun, J. J. Urban, J. Guo, J.-L. Chen, D. Prendergast, M. Salmeron, G. A. Somorjai, J. Su, Science, 2023, 381, 857-861.
[34]	J.-C. Hao, R.-X. Zhang, M. Ren, J.-X. Zhao, Z.-H. Gao, L. Liu, Z.-X. Zhang, Z.-J. Zuo, Catalysts, 2023, 13, 868.
[35]	H. Xiong, Y. Dong, C. Hu, Y. Chen, H. Liu, R. Long, T. Kong, Y. Xiong, J. Am. Chem. Soc., 2024, 146, 9465-9475.
[36]	Z. Zhang, K. Feng, B. Yan, Catal. Sci. Technol., 2022, 12, 4698-4708.
[37]	Y. Xu, J. Yao, H. Lin, Q. Lv, B. Liu, L. Wu, L. Tan, Y. Dai, X. Zong, Y. Tang, ACS Catal., 2024, 14, 11845-11856.
[38]	N. Rui, X. Zhang, F. Zhang, Z. Liu, X. Cao, Z. Xie, R. Zou, S. D. Senanayake, Y. Yang, J. A. Rodriguez, C.-J. Liu, Appl. Catal. B, 2021, 282, 119581.
[39]	S. Tada, T. Shimizu, H. Kameyama, T. Haneda, R. Kikuchi, Int. J. Hydrogen Energy, 2012, 37, 5527-5531.
[40]	X. Du, D. Zhang, L. Shi, R. Gao, J. Zhang, J. Phys. Chem. C, 2012, 116, 10009-10016.
[41]	P. Du, G. Deng, Z. Li, J. Sun, L. Wang, Y. Yang, J. Wang, Y. Li, X. Xu, Y. Zhang, W. Liu, G. Liu, Z. Zou, Z. Li,, J. Mater. Sci. Technol., 2024, 189, 203-210.
[42]	C. Wang, L. Geng, Y. Bi, Nano-Micro Lett., 2025, 17, 184.
[43]	Y. Zhang, Z. Xu, G. Li, X. Huang, W. Hao, Y. Bi, Angew. Chem. Int. Ed., 2019, 58, 14229-14233.
[44]	V. Markoulaki Ι, I. Papadas, I. Kornarakis, G. Armatas, Nanomaterials, 2015, 5, 1971-1984.
[45]	M. Ashokkumar, S. Muthukumaran, J. Lumin., 2015, 162, 97-103.
[46]	J. Dhanalakshmi, S. Iyyapushpam, S. T. Nishanthi, M. Malligavathy, D. Pathinettam Padiyan, Adv. Nat. Sci: Nanosci. Nanotechnol., 2017, 8, 015015.
[47]	S.-Y. Yin, Z. Li, Y. Hu, X. Luo, J. Li, Green Energy Environ., 2024, 9, 1407-1418.
[48]	J. Xie, Y. Jiang, S. Li, P. Xu, Q. Zheng, X. Fan, H. Peng, Z. Tang, Acta Phys.-Chim. Sin., 2023, 39, 2306037.
[49]	M. Huang, S. Zhang, Y. Gan, J. Liu, Z. He, T. Lin, F. Yu, Y. Dai, Q. Niu, L. Zhong, Chem. Eur. J., 2023, 29, e202204031.
[50]	Y. Zeng, Z. Tang, X. Wu, A. Huang, X. Luo, G.-Q. Xu, Y. Zhu, S.-L. Wang, Appl. Catal. B, 2022, 306, 120919.
[51]	J. Zhao, T. Wang, J. Deng, C.-M. Shu, Q. Zeng, T. Guo, Y. Zhang, Energy, 2020, 209, 118494.
[52]	Y. Liu, N. Cui, P. Jia, W. Huang, Catalysts, 2020, 10, 131.
[53]	Z. Fan, W. Weng, J. Zhou, D. Gu, W. Xiao, J. Energy Chem., 2021, 58, 415-430.

CO₂-free hydrogen production from solar-driven photothermal catalytic decomposition of methane

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Xuelu He, Wenyan Ma, Siteng Zhu, Dan Li, Jia-Xing Jiang. The effect of electronic structure matching between building blocks in conjugated porous polymers on photocatalytic hydrogen evolution activity [J]. Chinese Journal of Catalysis, 2025, 73(6): 279-288.
[2]	Jindou Hu, Miaomiao Zhu, Zahid Ali Ghazi, Yali Cao. Restoration mechanism of photocatalytic H₂O₂/H₂ production stability of ZnO/ZnS S-scheme heterojunction [J]. Chinese Journal of Catalysis, 2025, 71(4): 319-329.
[3]	Dezheng Li, Huimin Liu, Xuewen Xiao, Manqi Zhao, Dehua He, Yiming Lei. Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane [J]. Chinese Journal of Catalysis, 2025, 70(3): 399-409.
[4]	Yu Huang, Lei Zou, Yuan-Biao Huang, Rong Cao. Photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane to alcohol [J]. Chinese Journal of Catalysis, 2025, 70(3): 207-229.
[5]	Yuan Xiang, Jin Zhang, Fei Huang, Nantian Xiao, Yiyi Fan, Junhao Zhang, Heng Zheng, Jinwei Chen, Fan Zhang. One-pot photothermal upcycling of polylactic acid to hydrogen and pyruvic acid [J]. Chinese Journal of Catalysis, 2024, 59(4): 149-158.
[6]	Cheng Yang, Xin Li, Mei Li, Guijie Liang, Zhiliang Jin. Anchoring oxidation co-catalyst over CuMn₂O₄/graphdiyne S-scheme heterojunction to promote eosin-sensitized photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2024, 56(1): 88-103.
[7]	Xin Kang, Qiangmin Yu, Tianhao Zhang, Shuqi Hu, Heming Liu, Zhiyuan Zhang, Bilu Liu. A perspective on interface engineering of transition metal dichalcogenides for high-current-density hydrogen evolution [J]. Chinese Journal of Catalysis, 2024, 56(1): 9-24.
[8]	Sikai Wang, Xiang-Ting Min, Botao Qiao, Ning Yan, Tao Zhang. Single-atom catalysts: In search of the holy grails in catalysis [J]. Chinese Journal of Catalysis, 2023, 52(9): 1-13.
[9]	Bowen Liu, Jiajie Cai, Jianjun Zhang, Haiyan Tan, Bei Cheng, Jingsan Xu. Simultaneous benzyl alcohol oxidation and H₂ generation over MOF/CdS S-scheme photocatalysts and mechanism study [J]. Chinese Journal of Catalysis, 2023, 51(8): 204-215.
[10]	Wei Qiao, Lice Yu, Jinfa Chang, Fulin Yang, Ligang Feng. Efficient bi-functional catalysis of coupled MoSe₂ nanosheet/Pt nanoparticles for methanol-assisted water splitting [J]. Chinese Journal of Catalysis, 2023, 51(8): 113-123.
[11]	Bo Zhou, Jianqiao Shi, Yimin Jiang, Lei Xiao, Yuxuan Lu, Fan Dong, Chen Chen, Tehua Wang, Shuangyin Wang, Yuqin Zou. Enhanced dehydrogenation kinetics for ascorbic acid electrooxidation with ultra-low cell voltage and large current density [J]. Chinese Journal of Catalysis, 2023, 50(7): 372-380.
[12]	Xiangxi Lou, Xuan Gao, Yu Liu, Mingyu Chu, Congyang Zhang, Yinghua Qiu, Wenxiu Yang, Muhan Cao, Guiling Wang, Qiao Zhang, Jinxing Chen. Highly efficient photothermal catalytic upcycling of polyethylene terephthalate via boosted localized heating [J]. Chinese Journal of Catalysis, 2023, 49(6): 113-122.
[13]	Ning Li, Xueyun Gao, Junhui Su, Yangqin Gao, Lei Ge. Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis [J]. Chinese Journal of Catalysis, 2023, 47(4): 161-170.
[14]	Hua Liu, Leilei Kang, Hua Wang, Qike Jiang, Xiao Yan Liu, Aiqin Wang. Ru single-atom catalyst anchored on sulfated zirconia for direct methane conversion to methanol [J]. Chinese Journal of Catalysis, 2023, 46(3): 64-71.
[15]	Keran Wang, Lei Luo, Chao Wang, Junwang Tang. Photocatalytic methane activation by dual reaction sites co-modified WO₃ [J]. Chinese Journal of Catalysis, 2023, 46(3): 103-112.