Simultaneous value-added utilization of photogenerated electrons and holes via plasmon-exciton-phonon synergy in Mo2N QDs/ZnIn2S4 heterojunction

doi:10.1016/S1872-2067(26)64967-4

Abstract

Abstract:

The persistent challenge impeding photocatalytic advancement lies in achieving simultaneous efficient utilization of photogenerated carriers for dual value-added reactions. This study demonstrates the synergistic interplay of plasmon-exciton-phonon interactions within non-metallic plasmonic Mo₂N quantum dots anchored on ultrathin ZnIn₂S₄ nanosheets (0D/2D Mo₂N/ZnIn₂S₄), which simultaneously enhances photocatalytic hydrogen evolution and selective oxidation of 4-methoxybenzyl alcohol to 4-methoxybenzaldehyde. Integrated experimental, operando spectroscopic, and theoretical analyses reveal triple cooperative mechanisms: localized surface plasmon resonance at Mo₂N sites generates high-energy hot electrons through plasmon-exciton coupling, significantly reducing the apparent activation energy to 4.87 kJ·mol^-1; quantum confinement synergizing with the 0D/2D ohmic-junction concentrates excitons at nanoscale interfaces, enabling prolonged carrier lifetime; meanwhile, directional photon-to-phonon energy conversion induces uniform photothermal heating (ΔT = 55.9 °C), kinetically accelerating dehydrogenation while balancing redox half-reactions. This synergy achieves sacrificial-free co-production rates of 96.3 mmol·h^-1·g^-1 H₂ and 38.7 mmol·h^-1·g^-1 4-methoxybenzaldehyde with 13.7% apparent quantum efficiency at 420 nm, establishing a new paradigm for solar-driven chemical refineries via precision plasmon-phonon engineering.

Key words: Photocatalysis, H₂ evolution, 4-Methoxybenzyl alcohol oxidation, Localized surface plasmon resonance, Photon-phonon cooperativity

Jinhe Li, Xiaxi Yao, Xiaohui Yu, Xiaosong Zhou, Wei Ren, Lele Wang, Weikang Wang, Qinqin Liu. Simultaneous value-added utilization of photogenerated electrons and holes via plasmon-exciton-phonon synergy in Mo₂N QDs/ZnIn₂S₄ heterojunction[J]. Chinese Journal of Catalysis, 2026, 83: 219-230.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64967-4

https://www.cjcatal.com/EN/Y2026/V83/I4/219

Figures/Tables 7

Fig. 1. (a) Schematic synthesis of Mo2N/ZIS. TEM (b) and HRTEM (c) images of Mo2N. (d) HRTEM image of Mo2N/ZIS. (e) EDX images of Mo2N/ZIS.

Fig. 2. (a) XRD patterns of ZIS and MNZIS-5. In-situ high-resolution XPS spectra of S 2p (b), In 3d (c), Zn 2p (d), Mo 3d (e), and N 1s (f).

Fig. 3. Work functions of ZIS (a) and Mo2N (b). (c) Plane-averaged electron density differences along the Z-direction of Mo2N/ZIS composite. (d) Differential charge density (yellow represents electron accumulation; cyan represents electron dissipation). 2D charge density difference maps (e) and illustration in Mo2N/ZIS (f).

Fig. 4. H2 (a) and 4-MBAL (b) production rates of ZIS and composite with different Mo2N ratios. H2 (c) and 4-MBAL (d) production rates of ZIS and MNZIS-5 under different condition. (e) Comparison of H2 evolution between MNZIS-5 and reported literature. (f) Temperature dependence of 4-MBAL production rate for ZIS and MNZIS-5. Infrared thermograms at different irradiation times (g) and UV-vis DRS (h) of ZIS, Mo2N, and MNZIS-5.

Fig. 5. Surface charge density (a), surface photovoltage (b), IEF strength (c), electrochemical impedance spectroscopy(d), photocurrents (e), PL spectra (f), time-resolved photoluminescence spectra (g), open-circuit potential (h) and electron spin resonance (i) of ZIS and MNZIS-5.

Fig. 6. fs-TA of ZIS (a) and MNZIS-5 (b). Kinetic profiles of ZIS (c) and MNZIS-5 (d). (e) Scheme of the decay pathways of photoinduced electrons and hot-exciton production in ZIS and MNZIS-5.

Fig. 7. (a) In-situ DRIFTS of MNZIS-5. (b) Reaction pathways of 4-MBA oxidation on Mo2N and Mo2N/ZIS by DFT calculation. (c) Schematic illustration of H2 and 4-MBAL production over Mo2N/ZIS.

References

[1]	S. Bhattacharjee, S. Linley, E. Reisner, Nat. Rev. Chem., 2024, 8, 87-105.
[2]	L. Sun, X. Yu, L. Tang, W. Wang, Q. Liu, Chin. J. Catal., 2023, 52, 164-175.
[3]	X. Yang, Z. Guo, Y. Xu, Z. Li, Y. Zhou, Z. Yang, Z. Zhou, Y. Gao, J. Zhang, Chem. Res. Chin. Univ., 2024, 40, 536-547.
[4]	Y. Xu, M. M. Hassan, S. Ali, H. Li, Q. Ouyang, Q. Chen, J. Agric. Food Chem., 2021, 69, 1667-1674.
[5]	J. Li, L. Sun, H. Jiang, L. Wang, Q. Liu, J. Alloys Compd., 2024, 1008, 176770.
[6]	H. Yu, X. Zhang, Q. Chen, P.-K. Zhou, F. Xu, H. Wang, X. Chen, Chem. Res. Chin. Univ., 2025, 41, 734-740.
[7]	F. Liu, B. Sun, Z. Liu, Y. Wei, T. Gao, G. Zhou, Chin. J. Catal., 2024, 64, 152-165.
[8]	T. Xu, J. Shi, K.-S. Peng, Y.-H. Hsu, Y.-C. Liu, S. Wang, H. Zhang, Y. Wang, G. Zhang, S.-F. Hung, K. Liu, X. Wang, Angew. Chem. Int. Ed., 2025, 64, e202513029.
[9]	J. Li, C. Jin, Y. Zhao, X. Yu, W. Ren, L. Sun, L. Wang, W. Wang, J. Zhang, J. Yang, Q. Liu, ACS Catal., 2025, 15, 12123-12132.
[10]	S. Cao, B. Zhong, C. Bie, B. Cheng, F. Xu, Acta Phys.-Chim. Sin., 2024, 40, 2307016.
[11]	Z. Yang, T. Huang, M. Li, X. Wang, X. Zhou, S. Yang, Q. Gao, X. Cai, Y. Liu, Y. Fang, Y. Wang, S. Zhang, S. Zhang, Adv. Mater., 2024, 36, 2313513.
[12]	H. Jiang, J. Shen, L. Sun, J. Li, W. Wang, L. Wang, Q. Liu, Green Chem., 2025, 27, 6989-7008.
[13]	P. Lu, B. Du, K. Liu, Z. Luo, A. Sikandaier, L. Diao, J. Sun, L. Jiang, Y. Zhu, Chin. J. Struct. Chem., 2024, 43, 100361.
[14]	L. Jiao, D. Zhang, Z. Hao, F. Yu, X.-J. Lv, ACS Catal., 2021, 11, 8727-8735.
[15]	C. Han, Z. Zeng, X. Zhang, Y. Liang, B. K. Kundu, L. Yuan, C.-L. Tan, Y. Zhang, Y.-J. Xu, Angew. Chem. Int. Ed., 2024, 63, e202408527.
[16]	Y.-W. Han, Y.-T. Chu, L. Ye, T.-J. Gong, X.-B. Lu, Y. Fu, Adv. Funct. Mater., 2025, 35, 2411991.
[17]	Y. Wang, S. Sun, Q. Fan, N. Sirotkin, A. Agafonov, H. Zhu, Y. Teng, B. Yu, G. Liang, X. Xiong, J. Mater. Sci. Technol., 2026, 251, 135-148.
[18]	Y. Feng, S. Gong, Y. Wang, C. Ban, X. Qu, J. Ma, Y. Duan, C. Lin, D. Yu, L. Xia, X. Chen, X. Tao, L. Gan, X. Zhou, Adv. Mater., 2025, 37, 2412965.
[19]	S. Li, J. Li, W. Ren, Y. Xu, Q. Liu, J. Colloid Interface Sci., 2025, 691, 137462.
[20]	X. Zhang, Y. Jiang, H. Gu, H. Zhang, Y. Li, Z. Lu, S. Zhang, J. Liu, J. Zhang, Z. Tang, Nat. Commun., 2025, 16, 7612.
[21]	Y. Tang, Y. Guo, B. Liu, Y. Li, Z. Hu, X. Tan, J. Ye, T. Yu, Adv. Energy Mater., 2025, 15, 2501159.
[22]	X. Niu, X. Lu, B. He, X. Xiao, S. Wang, Z. Liang, Q. Shi, L.-F. Ma, Appl. Catal. B, 2025, 361, 124703.
[23]	X. Wan, Y. Li, Y. Chen, J. Ma, Y.-A. Liu, E.-D. Zhao, Y. Gu, Y. Zhao, Y. Cui, R. Li, D. Liu, R. Long, K. M. Liew, Y. Xiong, Nat. Commun., 2024, 15, 1273.
[24]	C. Xu, Q. Tang, W. Tu, L. Wang, Energy Environ. Sci., 2024, 17, 4461-4480.
[25]	Z. Chen, Y. Yan, K. Sun, L. Tan, F. Guo, X. Du, W. Shi, J. Colloid Interface Sci., 2024, 661, 12-22.
[26]	J. Xu, C. Fu, Q. Zhu, H. Zou, L. Wang, R. Yang, Z. Chen, H. Zhao, ACS Nano, 2025, 19, 26065-26074.
[27]	R. Li, Q. Shi, L. Zuo, Y. Chen, W. Li, H. Fan, B. Li, L. Wang, Int. J. Hydrogen Energy, 2023, 48, 8101-8114.
[28]	B. Ma, Y. Dang, D. Li, X. Wang, K. Lin, W. Wang, X. Zhou, Y. Chen, T. Xie, X. Zhang, H. Han, Appl. Catal. B, 2021, 298, 120491.
[29]	K. Lai, F. Li, N. Li, Y. Gao, L. Ge, Acta Phys.-Chim. Sin., 2024, 40, 2304018.
[30]	L. Xiao, W. Ren, S. Shen, M. Chen, R. Liao, Y. Zhou, X. Li, Acta Phys.-Chim. Sin., 2024, 40, 2308036.
[31]	B. Shao, T. Liu, D.B. Li, L. Meng, J. Wang, W. Zhai, L. Li, Adv. Mater., 2025, 37, 2504135.
[32]	J. Li, J. Yao, Q. Yu, X. Zhang, S. A. C. Carabineiro, X. Xiong, C. Wu, K. Lv, Appl. Catal. B, 2024, 351, 123950.
[33]	J. Chen, P. Bai, S. Yuan, Y. He, Z. Niu, Y. Zhao, Y. Li, Chin. J. Catal., 2024, 67, 124-134.
[34]	D. Ma, M. Xu, L. Ding, J. Guo, Y. Yang, W. Dou, H. Li, F. Chen, Y. Tang, Angew. Chem. Int. Ed., 2025, https://doi.org/10.1002/anie.202521029.
[35]	Z. Gao, A. Li, X. Liu, M. Peng, S. Yu, M. Wang, Y. Ge, C. Li, T. Wang, Z. Wang, W. Zhou, D. Ma, Nature, 2025, 638, 690-696.
[36]	Q. Hu, L. Chen, X. Xie, Z. Qin, H. Ji, T. Su, Acta Phys.-Chim. Sin., 2024, 40, 2406024.
[37]	S. Gong, Z. Jiang, P. Shi, J. Fan, Q. Xu, Y. Min, Appl. Catal. B, 2018, 238, 318-327.
[38]	Y. Zhao, C. Yang, S. Zhang, G. Sun, B. Zhu, L. Wang, J. Zhang, Chin. J. Catal., 2024, 63, 258-269.
[39]	B. Qi, R. Shen, Z. Ren, Y. Teng, H. Ding, X. Zhang, Y. Zhang, L. Hao, X. Li, J. Mater. Sci. Technol., 2025, 232, 65-73.
[40]	B. Feng, B. Qi, S. Wang, P. Zhang, R. Shen, Y. Li, X. Li, Energy Environ. Mater., 2025, e70153.
[41]	P. Dong, Y. Zhang, L. Zhang, L. Zhang, B. Zhang, J. Zhang, ACS Catal., 2025, 15, 18138-18154.
[42]	Z. Meng, J. Zhang, H. Long, H. García, L. Zhang, B. Zhu, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202505456.
[43]	Y. Teng, L.-L. Ning, C.-W. Tan, J. Zhao, Y.-W. Xiong, H.-L. Zou, Z.-M. Ye, X.-M. Zhang, D.-B. Kuang, Y. Li, Adv. Funct. Mater., 2025, 35, 2414892.
[44]	T. Yang, J. Wang, Z. Wang, J. Zhang, K. Dai, Chin. J. Catal., 2024, 58, 157-167.
[45]	Y. Shen, J. Shi, J. Lei, P. Shan, A. Bian, W. Kong, A. Proskurin, M. Wu, C. Lu, G. Wang, W. Shi, Chem. Eng. J., 2025, 508, 161072.
[46]	L. Sun, J. Gao, J. Shen, Z. Lu, H. Jiang, W. Wang, L. Wang, X. Yu, J. Yang, Q. Liu, Ceram. Int., 2024, 50, 53801-53811.
[47]	X. Zhu, Y. Jia, Y. Liu, J. Xu, H. He, S. Wang, Y. Shao, Y. Zhai, Y. Zhu, Angew. Chem. Int. Ed., 2024, 63, e202405962.
[48]	W. Li, J. Jing, Z. Wei, J. Xu, W. Shi, H. Wang, X. Zhu, Y. Du, Y. Wang, J. Li, Y. Zhu, JACS Au, 2025, 5, 3500-3512.
[49]	Z. Lu, J. Gao, S. Rao, C. Jin, H. Jiang, J. Shen, X. Yu, W. Wang, L. Wang, J. Yang, Q. Liu, Appl. Catal. B, 2024, 342, 123374.
[50]	H. Jiang, L. Wang, X. Yu, L. Sun, J. Li, J. Yang, Q. Liu, Chem. Eng. J., 2023, 466, 143129.
[51]	Z. Chen, H. Zhou, F. Kong, Z. Dou, J. Yang, M. Wang, Adv. Funct. Mater., 2024, 35, 2418154.
[52]	H. Jiang, J. Li, W. Ren, Z. Wang, L. Wang, W. Wang, J. Yang, Q. Liu, Appl. Catal. B, 2025, 378, 125638.
[53]	X. Ruan, M. Xu, X. Zhang, C. Ding, D. Meng, J. Leng, W. Zhang, S. K. Ravi, X. Cui, Adv. Energy Mater., 2025, 15, 2502302.
[54]	X. Xiang, B. Cheng, B. Zhu, C. Jiang, G. Liang, Chin. J. Catal., 2025, 68, 326-335.
[55]	P. Hu, J. Zhang, G. Liang, J. Yu, F. Xu, ACS Catal., 2024, 14, 15025-15035.
[56]	L. Li, Z. Chen, D. Fang, J. Low, J. Yi, Adv. Sci., 2025, 12, e00666.
[57]	W. Liu, J. Jiang, Z. Li, B. Gao, C. Liu, C. Liu, W. Hao, R. Fan, J. Liu, T. Yu, Z. Zou, Z. Li, Angew. Chem. Int. Ed., 2025, 64, e202507312.
[58]	R. Pan, X. Ge, Q. Liu, H. Yin, Y. Guo, J. Shen, D. Zhang, P. Chen, J. Yuan, H. Xie, C. Liu, Adv. Funct. Mater., 2024, 34, 2315212.
[59]	S. Gong, Y. Niu, X. Liu, C. Xu, C. Chen, T. J. Meyer, Z. Chen, ACS Nano, 2023, 17, 4922-4932.

Simultaneous value-added utilization of photogenerated electrons and holes via plasmon-exciton-phonon synergy in Mo₂N QDs/ZnIn₂S₄ heterojunction

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