Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

Zhe Yin; Min Hu; Jun Liu; Hao Fu; Zhijie Wang; Aiwei Tang

doi:10.1088/1674-4926/43/3/032701

J. Semicond. > 2022, Volume 43 > Issue 3 > 032701, doi: 10.1088/1674-4926/43/3/032701

ARTICLES

Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

Zhe Yin¹, Min Hu¹, Jun Liu^{2, 3}, Hao Fu¹, Zhijie Wang^{2, 3, 4,} and Aiwei Tang^1,

+ Author Affiliations

Corresponding author: Zhijie Wang, wangzj@semi.ac.cn; Aiwei Tang, awtang@bjtu.edu.cn

Abstract: Hydrogen energy is a powerful and efficient energy resource, which can be produced by photocatalytic water splitting. Among the photocatalysis, multinary copper-based chalcogenide semiconductor nanocrystals exhibit great potential due to their tunable crystal structures, adjustable optical band gap, eco-friendly, and abundant resources. In this paper, Cu–Zn–Sn–S (CZTS) nanocrystals with different Cu content have been synthesized by using the one-pot method. By regulating the surface ligands, the reaction temperature, and the Cu content, kesterite and hexagonal wurtzite CZTS nanocrystals were obtained. The critical factors for the controllable transition between two phases were discussed. Subsequently, a series of quaternary CZTS nanocrystals with different Cu content were used for photocatalytic hydrogen evolution. And their band gap, energy level structure, and charge transfer ability were compared comprehensively. As a result, the pure hexagonal wurtzite CZTS nanocrystals have exhibited an improved photocatalytic hydrogen evolution activity.

Key words: photocatalytic hydrogen evolution, wurtzite, Cu–Zn–Sn–S nanocrystals

References

[1]	Huang Y B, Liu J, Deng Y C, et al. The application of perovskite materials in solar water splitting. J Semicond, 2020, 41(1), 011701 doi: 10.1088/1674-4926/41/1/011701
[2]	Hoffmann M R, Martin S T, Choi W, et al. Environmental applications of semiconductor photocatalysis. Chem Rev, 1995, 95(1), 69 doi: 10.1021/cr00033a004
[3]	Wei W Q, Ouyang S X, Zhang T R. Perylene diimide self-assembly: From electronic structural modulation to photocatalytic applications. J Semicond, 2020, 41(9), 091708 doi: 10.1088/1674-4926/41/9/091708
[4]	Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358), 37 doi: 10.1038/238037a0
[5]	Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev, 2014, 43(22), 7520 doi: 10.1039/C3CS60378D
[6]	Fujishima A, Zhang X, Tryk D A. Heterogeneous photocatalysis: from water photolysis to applications in environmental cleanup. Int J Hydrogen Energ, 2007, 32(14), 2664 doi: 10.1016/j.ijhydene.2006.09.009
[7]	Chen S, Takata T, Domen K. Particulate photocatalysts for overall water splitting. Nat Rev Mater, 2017, 2(10), 17050 doi: 10.1038/natrevmats.2017.50
[8]	Low J, Yu J, Jaroniec M, et al. Heterojunction photocatalysts. Adv Mater, 2017, 29(20), 1601694 doi: 10.1002/adma.201601694
[9]	Huang Y, Liu J, Cao D, et al. Separation of hot electrons and holes in Au/LaFeO₃ to boost the photocatalytic activities both for water reduction and oxidation. Int J Hydrogen Energ, 2019, 44(26), 13242 doi: 10.1016/j.ijhydene.2019.03.182
[10]	Wang H, Wu Z, Liu Y, et al. The characterization of ZnO-anatase-rutile three-component semiconductor and enhanced photocatalytic activity of nitrogen oxides. J Mater Chem C, 2008, 287(1/2), 176 doi: 10.1016/j.molcata.2008.03.010
[11]	Logvinovich D, Bocher L, Sheptyakov D, et al. Microstructure, surface composition and chemical stability of partly ordered LaTiO₂N. Solid State Sci, 2009, 11(8), 1513 doi: 10.1016/j.solidstatesciences.2009.05.024
[12]	Bao N, Shen L, Takata T, et al. Self-templated synthesis of nanoporous CdS nanostructures for highly efficient photocatalytic hydrogen production under visible light. Chem Mater, 2008, 20(1), 110 doi: 10.1021/cm7029344
[13]	Liu Z, Zhao K, Tang A, et al. Solution-processed high-efficiency cadmium-free Cu-Zn-In-S-based quantum-dot light-emitting diodes with low turn-on voltage. Org Electron, 2016, 36, 97 doi: 10.1016/j.orgel.2016.05.040
[14]	Coughlan C, Ibanez M, Dobrozhan O, et al. Compound copper chalcogenide nanocrystals. Chem Rev, 2017, 117(9), 5865 doi: 10.1021/acs.chemrev.6b00376
[15]	Chang J, Waclawik E R. Colloidal semiconductor nanocrystals: controlled synthesis and surface chemistry in organic media. RSC Adv, 2014, 4(45), 23505 doi: 10.1039/C4RA02684E
[16]	Aldakov D, Lefrançois A, Reiss P. Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications. J Mater Chem C, 2013, 1(24), 3756 doi: 10.1039/c3tc30273c
[17]	Liu Z, Tang A, Wang M, et al. Heating-up synthesis of cadimum-free and color-tunable quaternary and five-component Cu-In-Zn-S-based semiconductor nanocrystals. J Mater Chem C, 2015, 3(39), 10114 doi: 10.1039/C5TC02469B
[18]	Fu H, Tang A. Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution. J Semicond, 2020, 41(9), 91706 doi: 10.1088/1674-4926/41/9/091706
[19]	Fan X B, Yu S, Zhan F, et al. Nonstoichiometric Cu_xIn_yS quantum dots for efficient photocatalytic hydrogen evolution. Chemsuschem, 2017, 10(24), 4833 doi: 10.1002/cssc.201701950
[20]	Schmidt S S, Abou-Ras D, Unold T, et al. Effect of Zn incorporation into CuInS₂ solar cell absorbers on microstructural and electrical properties. J Appl Phys, 2011, 110(6), 64515 doi: 10.1063/1.3639284
[21]	Li Y, Chen G, Wang Q, et al. Hierarchical ZnS-In₂S₃-CuS nanospheres with nanoporous structure: Facile synthesis, growth mechanism, and excellent photocatalytic activity. Adv Funct Mater, 2010, 20(19), 3390 doi: 10.1002/adfm.201000604
[22]	Zhu D, Ye H, Liu Z, et al. Seed-mediated growth of heterostructured Cu_1.94S–MS (M = Zn, Cd, Mn) and alloyed CuNS₂ (N = In, Ga) nanocrystals for use in structure-and composition-dependent photocatalytic hydrogen evolution. Nanoscale, 2020, 12(10), 6111 doi: 10.1039/C9NR10004K
[23]	Saldanha P L, Brescia R, Prato M, et al. Generalized one-pot synthesis of copper sulfide, selenide-sulfide, and telluride-sulfide nanoparticles. Chem Mater, 2014, 26(3), 1442 doi: 10.1021/cm4035598
[24]	Zhu D, Tang A, Kong Q, et al. Roles of sulfur sources in the formation of alloyed Cu_{2– x}S_ySe_{1– y} nanocrystals: Controllable synthesis and tuning of plasmonic resonance absorption. J Phys Chem C, 2017, 121(29), 15922 doi: 10.1021/acs.jpcc.7b03826
[25]	Kuzuya T, Hamanaka Y, Itoh K, et al. Phase control and its mechanism of CuInS₂ nanoparticles. J Colloid Interf Sci, 2012, 388(1), 137 doi: 10.1016/j.jcis.2012.08.013
[26]	Liu Z, Liu J, Huang Y, et al. From one-dimensional to two-dimensional wurtzite CuGaS₂ nanocrystals: non-injection synthesis and photocatalytic evolution. Nanoscale, 2019, 11(1), 158 doi: 10.1039/C8NR07353H
[27]	Liu Z, Tang A, Liu J, et al. Non-injection synthesis of L-shaped wurtzite Cu–Ga–Zn–S alloyed nanorods and their advantageous application in photocatalytic hydrogen evolution. J Mater Chem A, 2018, 6(38), 18649 doi: 10.1039/C8TA05395B

Fig. 1. (Color online) (a) Schematic illustration of one-pot synthesis of CZTS nanocrystals. XRD patterns of CZTS nanocrystals obtained at (b) low Cu content, (c) high Cu content. (d) TEM images of hexagonal wurtzite CZTS. The inset is an enlarged view. (e) SAED pattern of hexagonal wurtzite CZTS. (f) HRTEM images of hexagonal wurtzite CZTS nanocrystals in (002) crystal plane and (g) in (101) crystal plane.

DownLoad: Full-Size Img PowerPoint

Fig. 2. (Color online) (a) SEM-EDS element distribution diagram of hexagonal wurtzite CZTS nanocrystals. (b) The cation percentages of CTZS nanocrystals obtained from EDS results. XPS signals of (c) Cu, (d) Sn, (e) Zn, and (f) S elements in hexagonal wurtzite CZTS nanocrystals.

DownLoad: Full-Size Img PowerPoint

Fig. 3. (Color online) (a) Diffuse reflectance spectra and (b) the plots of (αhv)² versus the photon energy of CZTS nanocrystals with different Cu content. UPS spectra of (c) high-binding energy secondary-electron cutoff and (d) valence-band edge regions of hexagonal wurtzite CZTS nanocrystals. (e) Energy level structure diagram of hexagonal wurtzite CZTS nanocrystals.

DownLoad: Full-Size Img PowerPoint

Fig. 4. (Color online) (a) Photocurrent of CZTS nanocrystals with different Cu content. (b) Impedance spectra of CZTS nanocrystals with different Cu content. (c) Photocatalytic hydrogen evolution for hydrogen amount variation with time. (d) Photocatalytic hydrogen production rates.

DownLoad: Full-Size Img PowerPoint

Table 1. Summary of the energy level information of wurtzite CZTS nanocrystals.

Sample	E_cut-off (eV)	E_onset (eV)	VBM (eV)	Band gap (eV)	CBM (eV)
Wurtzite CZTS	17.68	1.28	4.82	1.74	3.08

DownLoad: CSV

[1]	Huang Y B, Liu J, Deng Y C, et al. The application of perovskite materials in solar water splitting. J Semicond, 2020, 41(1), 011701 doi: 10.1088/1674-4926/41/1/011701
[2]	Hoffmann M R, Martin S T, Choi W, et al. Environmental applications of semiconductor photocatalysis. Chem Rev, 1995, 95(1), 69 doi: 10.1021/cr00033a004
[3]	Wei W Q, Ouyang S X, Zhang T R. Perylene diimide self-assembly: From electronic structural modulation to photocatalytic applications. J Semicond, 2020, 41(9), 091708 doi: 10.1088/1674-4926/41/9/091708
[4]	Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358), 37 doi: 10.1038/238037a0
[5]	Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev, 2014, 43(22), 7520 doi: 10.1039/C3CS60378D
[6]	Fujishima A, Zhang X, Tryk D A. Heterogeneous photocatalysis: from water photolysis to applications in environmental cleanup. Int J Hydrogen Energ, 2007, 32(14), 2664 doi: 10.1016/j.ijhydene.2006.09.009
[7]	Chen S, Takata T, Domen K. Particulate photocatalysts for overall water splitting. Nat Rev Mater, 2017, 2(10), 17050 doi: 10.1038/natrevmats.2017.50
[8]	Low J, Yu J, Jaroniec M, et al. Heterojunction photocatalysts. Adv Mater, 2017, 29(20), 1601694 doi: 10.1002/adma.201601694
[9]	Huang Y, Liu J, Cao D, et al. Separation of hot electrons and holes in Au/LaFeO₃ to boost the photocatalytic activities both for water reduction and oxidation. Int J Hydrogen Energ, 2019, 44(26), 13242 doi: 10.1016/j.ijhydene.2019.03.182
[10]	Wang H, Wu Z, Liu Y, et al. The characterization of ZnO-anatase-rutile three-component semiconductor and enhanced photocatalytic activity of nitrogen oxides. J Mater Chem C, 2008, 287(1/2), 176 doi: 10.1016/j.molcata.2008.03.010
[11]	Logvinovich D, Bocher L, Sheptyakov D, et al. Microstructure, surface composition and chemical stability of partly ordered LaTiO₂N. Solid State Sci, 2009, 11(8), 1513 doi: 10.1016/j.solidstatesciences.2009.05.024
[12]	Bao N, Shen L, Takata T, et al. Self-templated synthesis of nanoporous CdS nanostructures for highly efficient photocatalytic hydrogen production under visible light. Chem Mater, 2008, 20(1), 110 doi: 10.1021/cm7029344
[13]	Liu Z, Zhao K, Tang A, et al. Solution-processed high-efficiency cadmium-free Cu-Zn-In-S-based quantum-dot light-emitting diodes with low turn-on voltage. Org Electron, 2016, 36, 97 doi: 10.1016/j.orgel.2016.05.040
[14]	Coughlan C, Ibanez M, Dobrozhan O, et al. Compound copper chalcogenide nanocrystals. Chem Rev, 2017, 117(9), 5865 doi: 10.1021/acs.chemrev.6b00376
[15]	Chang J, Waclawik E R. Colloidal semiconductor nanocrystals: controlled synthesis and surface chemistry in organic media. RSC Adv, 2014, 4(45), 23505 doi: 10.1039/C4RA02684E
[16]	Aldakov D, Lefrançois A, Reiss P. Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications. J Mater Chem C, 2013, 1(24), 3756 doi: 10.1039/c3tc30273c
[17]	Liu Z, Tang A, Wang M, et al. Heating-up synthesis of cadimum-free and color-tunable quaternary and five-component Cu-In-Zn-S-based semiconductor nanocrystals. J Mater Chem C, 2015, 3(39), 10114 doi: 10.1039/C5TC02469B
[18]	Fu H, Tang A. Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution. J Semicond, 2020, 41(9), 91706 doi: 10.1088/1674-4926/41/9/091706
[19]	Fan X B, Yu S, Zhan F, et al. Nonstoichiometric Cu_xIn_yS quantum dots for efficient photocatalytic hydrogen evolution. Chemsuschem, 2017, 10(24), 4833 doi: 10.1002/cssc.201701950
[20]	Schmidt S S, Abou-Ras D, Unold T, et al. Effect of Zn incorporation into CuInS₂ solar cell absorbers on microstructural and electrical properties. J Appl Phys, 2011, 110(6), 64515 doi: 10.1063/1.3639284
[21]	Li Y, Chen G, Wang Q, et al. Hierarchical ZnS-In₂S₃-CuS nanospheres with nanoporous structure: Facile synthesis, growth mechanism, and excellent photocatalytic activity. Adv Funct Mater, 2010, 20(19), 3390 doi: 10.1002/adfm.201000604
[22]	Zhu D, Ye H, Liu Z, et al. Seed-mediated growth of heterostructured Cu_1.94S–MS (M = Zn, Cd, Mn) and alloyed CuNS₂ (N = In, Ga) nanocrystals for use in structure-and composition-dependent photocatalytic hydrogen evolution. Nanoscale, 2020, 12(10), 6111 doi: 10.1039/C9NR10004K
[23]	Saldanha P L, Brescia R, Prato M, et al. Generalized one-pot synthesis of copper sulfide, selenide-sulfide, and telluride-sulfide nanoparticles. Chem Mater, 2014, 26(3), 1442 doi: 10.1021/cm4035598
[24]	Zhu D, Tang A, Kong Q, et al. Roles of sulfur sources in the formation of alloyed Cu_{2– x}S_ySe_{1– y} nanocrystals: Controllable synthesis and tuning of plasmonic resonance absorption. J Phys Chem C, 2017, 121(29), 15922 doi: 10.1021/acs.jpcc.7b03826
[25]	Kuzuya T, Hamanaka Y, Itoh K, et al. Phase control and its mechanism of CuInS₂ nanoparticles. J Colloid Interf Sci, 2012, 388(1), 137 doi: 10.1016/j.jcis.2012.08.013
[26]	Liu Z, Liu J, Huang Y, et al. From one-dimensional to two-dimensional wurtzite CuGaS₂ nanocrystals: non-injection synthesis and photocatalytic evolution. Nanoscale, 2019, 11(1), 158 doi: 10.1039/C8NR07353H
[27]	Liu Z, Tang A, Liu J, et al. Non-injection synthesis of L-shaped wurtzite Cu–Ga–Zn–S alloyed nanorods and their advantageous application in photocatalytic hydrogen evolution. J Mater Chem A, 2018, 6(38), 18649 doi: 10.1039/C8TA05395B

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Received: 08 September 2021 Revised: 06 October 2021 Online: Uncorrected proof: 16 November 2021Accepted Manuscript: 16 November 2021Published: 10 March 2022

Article Navigation > Journal of Semiconductors > 2022 > 43(3): 032701

Zhe Yin, Min Hu, Jun Liu, Hao Fu, Zhijie Wang, Aiwei Tang. Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. Journal of Semiconductors, 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701 Z Yin, M Hu, J Liu, H Fu, Z J Wang, A W Tang, Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. J. Semicond., 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701.Export: BibTex EndNote

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Z Yin, M Hu, J Liu, H Fu, Z J Wang, A W Tang, Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. J. Semicond., 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701.

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Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

doi: 10.1088/1674-4926/43/3/032701

Zhe Yin¹,
Min Hu¹,
Jun Liu^2,3,
Hao Fu¹,
Zhijie Wang^2,3,4,,
Aiwei Tang^1,

1.
Key Laboratory of Luminescence and Optical Information, Ministry of Education, School of Science, Beijing Jiaotong University, Beijing 100044, China
2.
Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China
3.
Beijing Key Laboratory of Low Dimensional Semiconductor Materials and Devices, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China
4.
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

More Information

Author Bio:
Zhe Yin received her PhD degree from Tsinghua University in 2020. Then she joined Beijing Jiaotong University as a lecturer. Her research includes synthesizing of copper-based chalcogenide nanocrystals, lead-free perovskites, and exploring their application in flexible optoelectronics

Aiwei Tang is a full professor at the School of Science in Beijing Jiaotong University. He received his PhD degree from Beijing Jiaotong University in 2009. He then spent two years at the Institute of Semiconductors at the Chinese Academy of Sciences as a postdoctoral researcher. He joined Beijing Jiaotong University in 2011. His recent research interests are mainly focused on design of low-dimensional semiconductor nanomaterials and their optoelectronic applications
Corresponding author: wangzj@semi.ac.cn; awtang@bjtu.edu.cn
Received Date: 2021-09-08
Revised Date: 2021-10-06
Published Date: 2022-03-10

Abstract

Abstract

Hydrogen energy is a powerful and efficient energy resource, which can be produced by photocatalytic water splitting. Among the photocatalysis, multinary copper-based chalcogenide semiconductor nanocrystals exhibit great potential due to their tunable crystal structures, adjustable optical band gap, eco-friendly, and abundant resources. In this paper, Cu–Zn–Sn–S (CZTS) nanocrystals with different Cu content have been synthesized by using the one-pot method. By regulating the surface ligands, the reaction temperature, and the Cu content, kesterite and hexagonal wurtzite CZTS nanocrystals were obtained. The critical factors for the controllable transition between two phases were discussed. Subsequently, a series of quaternary CZTS nanocrystals with different Cu content were used for photocatalytic hydrogen evolution. And their band gap, energy level structure, and charge transfer ability were compared comprehensively. As a result, the pure hexagonal wurtzite CZTS nanocrystals have exhibited an improved photocatalytic hydrogen evolution activity.
- photocatalytic hydrogen evolution,
- wurtzite,
- Cu–Zn–Sn–S nanocrystals

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References(27)

References

[1]	Huang Y B, Liu J, Deng Y C, et al. The application of perovskite materials in solar water splitting. J Semicond, 2020, 41(1), 011701 doi: 10.1088/1674-4926/41/1/011701
[2]	Hoffmann M R, Martin S T, Choi W, et al. Environmental applications of semiconductor photocatalysis. Chem Rev, 1995, 95(1), 69 doi: 10.1021/cr00033a004
[3]	Wei W Q, Ouyang S X, Zhang T R. Perylene diimide self-assembly: From electronic structural modulation to photocatalytic applications. J Semicond, 2020, 41(9), 091708 doi: 10.1088/1674-4926/41/9/091708
[4]	Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358), 37 doi: 10.1038/238037a0
[5]	Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev, 2014, 43(22), 7520 doi: 10.1039/C3CS60378D
[6]	Fujishima A, Zhang X, Tryk D A. Heterogeneous photocatalysis: from water photolysis to applications in environmental cleanup. Int J Hydrogen Energ, 2007, 32(14), 2664 doi: 10.1016/j.ijhydene.2006.09.009
[7]	Chen S, Takata T, Domen K. Particulate photocatalysts for overall water splitting. Nat Rev Mater, 2017, 2(10), 17050 doi: 10.1038/natrevmats.2017.50
[8]	Low J, Yu J, Jaroniec M, et al. Heterojunction photocatalysts. Adv Mater, 2017, 29(20), 1601694 doi: 10.1002/adma.201601694
[9]	Huang Y, Liu J, Cao D, et al. Separation of hot electrons and holes in Au/LaFeO₃ to boost the photocatalytic activities both for water reduction and oxidation. Int J Hydrogen Energ, 2019, 44(26), 13242 doi: 10.1016/j.ijhydene.2019.03.182
[10]	Wang H, Wu Z, Liu Y, et al. The characterization of ZnO-anatase-rutile three-component semiconductor and enhanced photocatalytic activity of nitrogen oxides. J Mater Chem C, 2008, 287(1/2), 176 doi: 10.1016/j.molcata.2008.03.010
[11]	Logvinovich D, Bocher L, Sheptyakov D, et al. Microstructure, surface composition and chemical stability of partly ordered LaTiO₂N. Solid State Sci, 2009, 11(8), 1513 doi: 10.1016/j.solidstatesciences.2009.05.024
[12]	Bao N, Shen L, Takata T, et al. Self-templated synthesis of nanoporous CdS nanostructures for highly efficient photocatalytic hydrogen production under visible light. Chem Mater, 2008, 20(1), 110 doi: 10.1021/cm7029344
[13]	Liu Z, Zhao K, Tang A, et al. Solution-processed high-efficiency cadmium-free Cu-Zn-In-S-based quantum-dot light-emitting diodes with low turn-on voltage. Org Electron, 2016, 36, 97 doi: 10.1016/j.orgel.2016.05.040
[14]	Coughlan C, Ibanez M, Dobrozhan O, et al. Compound copper chalcogenide nanocrystals. Chem Rev, 2017, 117(9), 5865 doi: 10.1021/acs.chemrev.6b00376
[15]	Chang J, Waclawik E R. Colloidal semiconductor nanocrystals: controlled synthesis and surface chemistry in organic media. RSC Adv, 2014, 4(45), 23505 doi: 10.1039/C4RA02684E
[16]	Aldakov D, Lefrançois A, Reiss P. Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications. J Mater Chem C, 2013, 1(24), 3756 doi: 10.1039/c3tc30273c
[17]	Liu Z, Tang A, Wang M, et al. Heating-up synthesis of cadimum-free and color-tunable quaternary and five-component Cu-In-Zn-S-based semiconductor nanocrystals. J Mater Chem C, 2015, 3(39), 10114 doi: 10.1039/C5TC02469B
[18]	Fu H, Tang A. Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution. J Semicond, 2020, 41(9), 91706 doi: 10.1088/1674-4926/41/9/091706
[19]	Fan X B, Yu S, Zhan F, et al. Nonstoichiometric Cu_xIn_yS quantum dots for efficient photocatalytic hydrogen evolution. Chemsuschem, 2017, 10(24), 4833 doi: 10.1002/cssc.201701950
[20]	Schmidt S S, Abou-Ras D, Unold T, et al. Effect of Zn incorporation into CuInS₂ solar cell absorbers on microstructural and electrical properties. J Appl Phys, 2011, 110(6), 64515 doi: 10.1063/1.3639284
[21]	Li Y, Chen G, Wang Q, et al. Hierarchical ZnS-In₂S₃-CuS nanospheres with nanoporous structure: Facile synthesis, growth mechanism, and excellent photocatalytic activity. Adv Funct Mater, 2010, 20(19), 3390 doi: 10.1002/adfm.201000604
[22]	Zhu D, Ye H, Liu Z, et al. Seed-mediated growth of heterostructured Cu_1.94S–MS (M = Zn, Cd, Mn) and alloyed CuNS₂ (N = In, Ga) nanocrystals for use in structure-and composition-dependent photocatalytic hydrogen evolution. Nanoscale, 2020, 12(10), 6111 doi: 10.1039/C9NR10004K
[23]	Saldanha P L, Brescia R, Prato M, et al. Generalized one-pot synthesis of copper sulfide, selenide-sulfide, and telluride-sulfide nanoparticles. Chem Mater, 2014, 26(3), 1442 doi: 10.1021/cm4035598
[24]	Zhu D, Tang A, Kong Q, et al. Roles of sulfur sources in the formation of alloyed Cu_{2– x}S_ySe_{1– y} nanocrystals: Controllable synthesis and tuning of plasmonic resonance absorption. J Phys Chem C, 2017, 121(29), 15922 doi: 10.1021/acs.jpcc.7b03826
[25]	Kuzuya T, Hamanaka Y, Itoh K, et al. Phase control and its mechanism of CuInS₂ nanoparticles. J Colloid Interf Sci, 2012, 388(1), 137 doi: 10.1016/j.jcis.2012.08.013
[26]	Liu Z, Liu J, Huang Y, et al. From one-dimensional to two-dimensional wurtzite CuGaS₂ nanocrystals: non-injection synthesis and photocatalytic evolution. Nanoscale, 2019, 11(1), 158 doi: 10.1039/C8NR07353H
[27]	Liu Z, Tang A, Liu J, et al. Non-injection synthesis of L-shaped wurtzite Cu–Ga–Zn–S alloyed nanorods and their advantageous application in photocatalytic hydrogen evolution. J Mater Chem A, 2018, 6(38), 18649 doi: 10.1039/C8TA05395B

Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

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Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

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Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

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