Anchoring oxidation co-catalyst over CuMn2O4/graphdiyne S-scheme heterojunction to promote eosin-sensitized photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(23)64563-2

Abstract

Abstract:

It is widely acknowledged that efficient charge separation and utilization of photocatalysts are key factors in determing the photocatalytic hydrogen production. Construction of heterojunction has been considered as a promising way to efficiently solve the spatial separation of photogenerated charges. In addition, the introduction of proper cocatalysts can realize the separation of electrons and holes of the photocatalyst and enhance the photocatalytic performance by promoting more carriers to flow to the corresponding active sites. Herein, the S-scheme heterojunction was constructed by introducing graphdiyne into CuMn₂O₄ for photocatalytic hydrogen evolution. Graphdiyne as a reduction semiconductor and in situ produced Mn₂O₃ from CuMn₂O₄ as an oxidation cocatalyst to promote the precisely migration of photogenerated electrons and holes to the corresponding reduction and oxidation sites of photocatalyst. Notably, the photocatalytic performance of the 600-CuMn₂O₄/GDY-40%（6-CG-40%）could reach 1586.54 μmol g^-1 h^-1, which is 13.86 and 21.48 times higher than those of CuMn₂O₄ (106.73 μmol g^-1 h^-1) and graphdiyne (70.57 μmol g^-1 h^-1), respectively. Theoretical calculations and experiments results show that both in-situ induced growth of Mn₂O₃ oxidation co-catalyst and the introduction of graphdiyne to construct S-scheme heterojunction efficiently suppress the severe recombination of photogenerated electron-hole pairs, thus optimizing the photogenerated carrier transfer efficiency, and ultimately leading to the enhanced eosin Y-sensitized photocatalytic hydrogen evolution activity. This work provides a promising method for the construction of oxidation cocatalyst engineered S-scheme heterojunction for solar water splitting.

Key words: Graphdiyne, Oxidation co-catalyst, Charge separation, S-scheme heterojunction, Photocatalytic hydrogen production

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: 88-103.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64563-2

https://www.cjcatal.com/EN/Y2024/V56/I1/88

Figures/Tables 17

Fig. 1. Preparation roadmap of composite photocatalysts.

Fig. 2. Theoretical model of the GDY (a), CuMn2O4 (b) and Mn2O3 (c). XRD patterns of the GDY (d), CuMn2O4, 400-CuMn2O4, 600-CuMn2O4, 800-CuMn2O4 (e) and 6-CG-20%, 6-CG-30%, 6-CG-40%, 6-CG-50% (f). FTIR spectra (g) and Raman spectrum (h) of GDY. (i) Zeta potentials of GDY, CuMn2O4 and 6-CG-40%.

Fig. 3. SEM image of GDY (a), CuMn2O4 (b) and 6-CG-40% (c). TEM image of GDY (d), CuMn2O4 (e) and 6-CG-40% (f). HRTEM image of 6-CG-40% (g), EDX of 6-CG-40% (h).

Table 1 TEM element mapping content analysis of 6-CG-40%.

Element	k-factor	wt%	wt% Sigma
C	2.78081	4.74	0.15
O	2.02796	13.00	0.19
Mn	1.14436	31.00	0.17
Cu	1.23021	51.26	0.20
Total content		100.00

Table 2 BET Surface area (SBET), pore diameter and pore volume of CuMn2O4 and 6-CG-40%.

Samples	S_BET (m² g^-1)	Pore volume (cm³ g^-1)	Average pore size (nm)
CuMn₂O₄	6.89	0.03	20.77
6-CG-40%	15.00	0.11	41.32

Fig. 4. Nitrogen adsorption and desorption curves (a), pore size distribution curves (b) of CuMn2O4 and 6-CG-40%.

Fig. 5. XPS spectra of full spectrum (a), Cu 2p (b), Mn 2p (c), O 1s (d) and C 1s (e). (f) The LMM of Cu 2p.

Fig. 6. Photocatalytic hydrogen evolution activities of 400-CuMn2O4, 600-CuMn2O4, 800-CuMn2O4 (a), GDY, 600-CuMn2O4 and 6-CG-40% (b), 6-CG-20%, 6-CG-30%, 6-CG-40%, 6-CG-50% (c), 6-CG-40% in different pH environments (d), 6-CG-40% in different eosinY environments (e). (f) Cyclability of 6-CG-40%.

Fig. 7. UV-vis DRS spectra (a), PL spectra (b) and TRPL spectra (c) of GDY, CuMn2O4 and 6-CG-40%.

Table 3 Attenuation parameters photocatalyst.

Sample	Pre-exponential factor A	Lifetime τ (ns)	Average lifetime τ (ns)	χ²
EY	A₁ = 5.94, A₂ = 94.06	τ₁ = 0.1143, τ₂ = 0.0035	0.407	1.33
GDY	A₁ = 93.83, A₂ = 6.17	τ₁ = 0.0043, τ₂ = 0.1052	0.405	1.37
CuMn₂O₄	A₁ = 5.12, A₂ = 94.88	τ₁ = 0.1342, τ₂ = 0.0037	0.365	1.38
6-CG-40%	A₁ = 86.96, A₂ = 9.32, A₃ = 3.72	τ₁ = 0.0106, τ₂ = 0.0817, τ₃ = 0.2391	0.348	1.35

Fig. 8. Transient photocurrent response curve (a), EIS curve (b,c), LSV curve (d), CV curve (e) and Tafel curves (f) of GDY, CuMn2O4 and 6-CG-40%.

Fig. 9. TGA and DTG curves of GDY (a), CuMn2O4 (b), and 6-CG-40% (c).

Fig. 10. Contact Angle test diagram of GDY (a), CuMn2O4 (b) and 6-CG-40% (c). Contact angle simulation diagram of GDY (d), CuMn2O4 (e) and 6-CG-40% (f).

Fig. 11. Band structure diagram of GDY (a), CuMn2O4 (b), and Mn2O3 (c). Density of state diagram GDY (d), CuMn2O4 (e), and Mn2O3 (f).

Fig. 12. In-situ irradiation XPS spectra of Cu 2p (a), Mn 2p (b), O 1s (c), and C 1s (d) in 6-CG-40%.

Fig. 13. Band gap of GDY (a) and CuMn2O4 (b). Mott-Schottky plots of GDY (c) and CuMn2O4 (d). Ultraviolet photoelectron spectra of GDY (e) and CuMn2O4 (f). (g) The proposed charge transfer and separation mechanism of 6-CG-40%.

Fig. 14. Mechanism of photocatalytic hydrogen evolution for 6-CG-40%.

References

[1]	T. Li, Y. J. Li, Z. L. Jin, Inorg. Chem., 2022, 61, 12809-12821.
[2]	L. J. Zhang, X. Q. Hao, J. K. Li, Y. P. Wang, Z. L. Jin, Chin. J. Catal., 2020, 41, 82-94.
[3]	M. I. Hoffert, K. Caldeira, G. Benford, D. R. Criswell, C. Green, H. Herzog, A. K. Jain, H. S. Kheshgi, K. S. Lackner, J. S. Lewis, H. D. Lightfoot, W. Manheimer, J. C. Mankins, M. E. Mauel, L. J. Perkins, M. E. Schlesinger, T. Volk, T. M. L. Wigley, Science, 2002, 298, 981-987.
[4]	H. Y. Li, H. M. Gong, Z. L. Jin, Appl. Catal. B, 2022, 307, 121166.
[5]	Z. L. Jin, Y. L. Wu, Appl. Catal. B, 2023, 327, 122461.
[6]	J. H. Peng, X. Wang, Z. Wang, B. Liu, P. Zhang, X. Li, N. Li, Chin. J. Struct. Chem., 2022, 41, 2209094-2209104.
[7]	L. J. Zhang, Y. L. Wu, N. Tsubaki, Z. L. Jin, Acta Phys.-Chim. Sin., 2023, 39, 2302051.
[8]	R. Q. Gao, H. He, J. X. Bai, L. Hao, R. C. Shen, P. Zhang, Y. J. Li, X. Li, Chin. J. Struct. Chem., 2022, 41, 2206031-2206038.
[9]	R. Shen, L. Hao, Y. H. Ng, P. Zhang, A. Arramel, Y. Li, X. Li, Chin. J. Catal., 2022, 43, 2453-2483.
[10]	X. N. Wang, F. L. Wang, Y. H. Sang, H. Liu, Adv. Energy Mater., 2017, 7, 1700473.
[11]	Z. L. Jin, Y. B. Li, X. Q. Hao, Acta Phys.-Chim. Sin., 2021, 37, 1912033.
[12]	J. J. Zhang, L. Y. Zhang, W. Wang, J. G. Yu, J. Phys. Chem. Lett., 2022, 13, 8462-8469.
[13]	S. C. Liu, K. Wang, M. X. Yang, Z. L. Jin, Acta Phys.-Chim. Sin., 2022, 38, 2109023.
[14]	R. C. Shen, L. Hao, Q. Chen, Q. Q. Zheng, P. Zhang, X. Li, Acta Phys.-Chim. Sin., 2022, 38, 2110014.
[15]	Y. L. Wu, Y. J. Li, L. J. Zhang, Z. L. Jin, ChemCatChem, 2022, 14, e202101656.
[16]	T. Yan, X. J. Zhang, H. Liu, Z. L. Jin, Chin. J. Struct. Chem., 2022, 41, 2201047-2201053.
[17]	Z. L. Jin, H. Y. Li, J. K. Li, Chin. J. Catal., 2022, 43, 303-315.
[18]	X. P. Wang, Z. L. Jin, X. Li, Rare Metals, 2023, 42, 1494-1507.
[19]	M. J. Allen, V. C. Tung, R. B. Kaner, Chem. Rev., 2010, 110, 132-145.
[20]	R. H. Baughman, Science, 2002, 297, 787-792.
[21]	H. W. Kroto, J. R. Heath, S. C. O’ Brien, R. F. Curl, R. E. Smalley, Nature, 1985, 318, 162-163.
[22]	U. H. F. Bunz, Y. Rubin, Y. Tobe, Chem. Soc. Rev., 1999, 28, 107-119.
[23]	Y. Li, J. He, H. Shen, Chem.-Eur. J., 2020, 26, 12310-12321.
[24]	J. M. Chen, J. Y. Xi, D. Wang, Z. G. Shuai, J. Phys. Chem. Lett., 2013, 4, 1443-1448.
[25]	A. Torres-Pinto, C. G. Silva, J. L. Faria, A. M. T. Silva, Adv. Sci., 2021, 8, 2003900.
[26]	R. H. Baughman, H. Eckhardt, M. Kertesz, J. Chem. Phys., 1987, 87, 6687-6699.
[27]	G. X. Li, Y. L. Li, H. B. Liu, Y. B. Guo, Y. J. Li, D. B. Zhu, Chem. Commun., 2010, 46, 3256-3258.
[28]	T. Li, N. Tsubaki, Z. L. Jin, J. Mater. Sci. Technol., 2024. 169, 82-104.
[29]	Z. L. Jin, J. Chin. Ceram. Soc., 2023, 51, 106-116.
[30]	C. P. Xie, X. L. Hu, Z. Y. Guan, X. D. Li, F. H. Zhao, Y. W. Song, Y. Li, X. F. Li, N. Wang, C. S. Huang, Angew. Chem. Int. Ed., 2020, 59, 13542-13546.
[31]	C. S. Huang, Y. L. Zhao, Y. L. Li, Adv. Mater., 2019, 31, 1904885.
[32]	R. Sakamoto, N Fukui, H. Maeda, R. Matsuoka, R. Toyoda, H. Nishihara, Adv. Mater., 2019, 31, 1804211.
[33]	Y. Y. Han, X. L. Lu, S. F. Tang, X. P. Yin, Z. W. Wei, T. B. Lu, Adv. Energy Mater., 2018, 8, 1703992.
[34]	B. Sriram, J. N. Baby, S. F Wang, M. George, X. B. Joseph, J. T. Tsai, ACS Appl. Electron. Mater., 2021, 3, 362-372.
[35]	K. L. He, R. C. Shen, L. Hao, Y. J. Li, P. Zhang, J. Z. Jiang, X. Li, Acta Phys.-Chim. Sin., 2022, 38, 2201021.
[36]	W. J. Sun, Y. J. Dong, X. P. Zhai, M. Y. Zhang, K. Li, Q. Wang, Y. Ding, Chem. Eng. J., 2022, 430, 132872.
[37]	Y. R. Xu, X. D. Zhu, H. Yan, P. P. Wang, M. S. Song, C. C. Ma, Z. R. Chen, J. Y. Chu, X. L. Liu, Z. Y. Lu, Chin. J. Catal., 2022, 43, 1111-1122.
[38]	Q. Zhao, Z. H. Yan, C. C. Chen, J. Chen, Chem. Rev., 2017, 117, 10121-10211.
[39]	Z. L. Jin, X. H. Li, T. Li, Y. J. Li, Langmuir, 2022, 38, 15632-15641.
[40]	K. C. Yang, T. X. Liu, D. Z. Xiang, Y. J. Li, Z. L. Jin, Sep. Purif. Technol., 2022, 298, 121564.
[41]	T. Wang, Z. L. Jin, J. Mater. Sci. Technol., 2023, 155, 132-141.
[42]	X. P. Wang, T. Li, X. Y. Wang, Z. L. Jin, J. Mater. Chem. C, 2023, 11, 1798-1811.
[43]	Z. L. Zhu, Q. Bai, S. Li, S. H. Li, M. H. Liu, F. L. Du, N. Sui, W. W. Yu, Small, 2020, 16, 2001440.
[44]	X. P. Yin, S. W. Luo, S. F. Tang, X. L. Lu, T. B. Lu, Chin. J. Catal., 2021 42, 1379-1386.
[45]	X. Q. Hao, D. Z. Xiang, Z. L. Jin, Dalton Trans., 2021, 50, 10501-10514.
[46]	D. Z. Xiang, X. Q. Hao, X. Guo, G. R. Wang, K. C. Yang, Z. L. Jin, Adv. Mater. Interfaces, 2022, 9, 2201400.
[47]	L. Cheng, X. Y. Yue, J. J. Fan, Q. J. Xiang, Adv. Mater., 2022, 34, 2200929.
[48]	Y. Yang, W. Z. Si, Y. Peng, Y. Wang, H. Liu, Z. Su, J. H. Li, Environ. Sci. Technol., 2022, 56, 16249-16258.
[49]	Y. Gao, B. Li, Z. Y. Zhang, X. F. Zhang, Z. P. Deng, L. H. Huo, S. Gao, ACS Appl. Nano Mater., 2021, 4, 6832-6843.
[50]	B. J. Rani, A. Sivanantham, T. S. Shridharan, T. Runfa, I. S. Cho, J. Mater. Chem. A, 2022, 10, 17710-17720.
[51]	H. Y. Li, H. M. Gong, Z. L. Jin. Acta Phys.-Chim. Sin., 2022, 38, 2201037.
[52]	Z. B. Fan, X. Guo, M. X. Yang, Z. L. Jin, Chin. J. Catal., 2022, 43, 2708-2719.
[53]	C. Yang, X. P. Wang, Y. L. Wu, Z. L. Jin, Chem. Eng. J., 2023, 470, 144424.
[54]	Z. H. Yu, X. Y. Yue, J. J. Fan, Q. J. Xiang, ACS Catal., 2022, 12, 6345-6358.
[55]	G. S. Zhou, Y. Cheng, Z. H. Yu, X. L. Liu, D. H. Chen, J. Q. Wang, Y. Hang, Y. R. Xu, C. X. Li, Z. Y. Lu, Chem. Commun., 2022, 58, 10036-10039.
[56]	T. Li, Z. L. Jin, J. Catal., 2023, 417, 274-285.
[57]	P. Y. Kuang, B. C. Zhu, Y. L. Li, H. B. Liu, J. G. Yu, K. Fan, Nanoscale Horiz., 2018, 3, 317-326.
[58]	L. Ding, W. Y. Yang, L. F. Chen, H. Y. Cheng, Z. W. Qi, Catal. Today, 2020, 347, 39-47.
[59]	X. Y. Meng, J. Y. Yang, C. C. Zhang, Y. F. Fu, K. Li, M. H. Sun, X. G. Wang, C. Z. Dong, B. C. Ma, Y. Ding, ACS Catal., 2022, 12, 89-100.
[60]	J. Yu, W. M. Chen, K. X. Li, C. H. Zhang, M. Z. Li, F. He, L. Jiang, Y. L. Li, W.G. Song, C. Y. Cao, Angew. Chem. Int. Ed., 2022, 61, e202207255.
[61]	L. B. Wang, B. Cheng, L. Y. Zhang, J. G. Yu, Small, 2021, 17, 2103447.
[62]	L. Y. Zhang, J. J. Zhang, H. G. Yu, J. G. Yu, Adv. Mater., 2022, 34, 2107668.
[63]	Y. Cao, H. Q. Gou, P. F. Zhu, Z. L. Jin, Chin. J. Struct. Chem., 2022, 41, 2206079-2206085.
[64]	Z. Y. Lu, G. S. Zhou, B. Li, Y. R. Xu, P. P. Wang, H. Yan, M. S. Song, C. C. Ma, S. Han, X. L. Liu, Appl. Catal. B, 2022, 301, 120787.
[65]	X. H. Li, Y. J. Li, X. Guo, Z. L. Jin, Front. Chem. Sci. Eng., 2023, 17, 606-616.
[66]	C. Yang, X. P. Wang, T. Li, Y. L. Wu, T. L. Hu, Z. L. Jin, Solar RRL, 2023, 7, 2300311.
[67]	Y. J. Dong,. Q. Y. Hu, B. N. Li, X. H. Li M., X. Chen, M. Y. Zhang,. Y. Feng, Y. Ding, Appl. Catal. B, 2022, 304, 120998.
[68]	J. Zou, G. D. Liao, J. Z. Jiang, Z. G. Xiong, S. S. Bai, H. T. Wang, P. X. Wu, P. Zhang, X. Li, Chin. J. Struct. Chem., 2022, 41, 2201025-2201033.
[69]	X. Y. Yue, J. J. Fan, Q. J. Xiang, Adv. Funct. Mater., 2022, 32, 2110258.
[70]	C. Yang, X. P. Wang, T. Li, Y. L. Wu, Z. L. Jin, Langmuir, 2023, 39, 9816-9830.

Anchoring oxidation co-catalyst over CuMn₂O₄/graphdiyne S-scheme heterojunction to promote eosin-sensitized photocatalytic hydrogen evolution

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

share this article

Figures/Tables 17

References

Related Articles 15

Recommended Articles

Metrics

[1]	Lijuan Sun, Xiaohui Yu, Liyong Tang, Weikang Wang, Qinqin Liu. Hollow dodecahedron K₃PW₁₂O₄₀/CdS core-shell S-scheme heterojunction for photocatalytic synergistic H₂ evolution and benzyl alcohol oxidation [J]. Chinese Journal of Catalysis, 2023, 52(9): 164-175.
[2]	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.
[3]	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.
[4]	Mingming Song, Xianghai Song, Xin Liu, Weiqiang Zhou, Pengwei Huo. Enhancing photocatalytic CO₂ reduction activity of ZnIn₂S₄/MOF-808 microsphere with S-scheme heterojunction by in situ synthesis method [J]. Chinese Journal of Catalysis, 2023, 51(8): 180-192.
[5]	Xiuli Shao, Ke Li, Jingping Li, Qiang Cheng, Guohong Wang, Kai Wang. Investigating S-scheme charge transfer pathways in NiS@Ta₂O₅ hybrid nanofibers for photocatalytic CO₂ conversion [J]. Chinese Journal of Catalysis, 2023, 51(8): 193-203.
[6]	Fei Yan, Youzi Zhang, Sibi Liu, Ruiqing Zou, Jahan B Ghasemi, Xuanhua Li. Efficient charge separation by a donor-acceptor system integrating dibenzothiophene into a porphyrin-based metal-organic framework for enhanced photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2023, 51(8): 124-134.
[7]	Bin Chen, Ya-Fei Jiang, Hai Xiao, Jun Li. Bimetallic single-cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction [J]. Chinese Journal of Catalysis, 2023, 50(7): 306-313.
[8]	Haibo Zhang, Zhongliao Wang, Jinfeng Zhang, Kai Dai. Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in-situ characterization [J]. Chinese Journal of Catalysis, 2023, 49(6): 42-67.
[9]	Houwei He, Zhongliao Wang, Kai Dai, Suwen Li, Jinfeng Zhang. LSPR-enhanced carbon-coated In₂O₃/W₁₈O₄₉ S-scheme heterojunction for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2023, 48(5): 267-278.
[10]	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.
[11]	Han Li, Shanren Tao, Sijie Wan, Guogen Qiu, Qing Long, Jiaguo Yu, Shaowen Cao. S-scheme heterojunction of ZnCdS nanospheres and dibenzothiophene modified graphite carbon nitride for enhanced H₂ production [J]. Chinese Journal of Catalysis, 2023, 46(3): 167-176.
[12]	Zhijie Zhang, Xuesheng Wang, Huiling Tang, Deben Li, Jiayue Xu. Modulation of Fermi level gap and internal electric field over Cs₃Bi₂Br₉@V_O-In₂O₃S-scheme heterojunction for boosted charge separation and CO₂ photoconversion [J]. Chinese Journal of Catalysis, 2023, 55(12): 227-240.
[13]	You Wu, Yi Yang, Miaoli Gu, Chuanbiao Bie, Haiyan Tan, Bei Cheng, Jingsan Xu. 1D/0D heterostructured ZnIn₂S₄@ZnO S-scheme photocatalysts for improved H₂O₂ preparation [J]. Chinese Journal of Catalysis, 2023, 53(10): 123-133.
[14]	Wen Zhang, Meng Tian, Haimiao Jiao, Hai-Ying Jiang, Junwang Tang. Conformal BiVO₄/WO₃ nanobowl array photoanode for efficient photoelectrochemical water splitting [J]. Chinese Journal of Catalysis, 2022, 43(9): 2321-2331.
[15]	Meiyu Zhang, Chaochao Qin, Wanjun Sun, Congzhao Dong, Jun Zhong, Kaifeng Wu, Yong Ding. Energy funneling and charge separation in CdS modified with dual cocatalysts for enhanced H₂ generation [J]. Chinese Journal of Catalysis, 2022, 43(7): 1818-1829.