具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢

doi:10.1016/S1872-2067(21)63864-0

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 782-792.DOI: 10.1016/S1872-2067(21)63864-0

具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢

黄俊敏, 陈健民, 刘望喜, 张静文, 陈俊英^*(), 李映伟^#()

华南理工大学化学与化工学院, 制浆造纸工程国家重点实验室, 广东广州 510640

收稿日期:2021-04-17 修回日期:2021-04-17 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: 陈俊英,李映伟
基金资助:
国家自然科学基金(21825802);国家自然科学基金(21706078);中央高校基本科研业务费(2019PY11);中央高校基本科研业务费(2019MS038);广州市科技计划项目(201804020009);广州市珠江科技新星计划(201906010001);广东省自然科学基金(2016A030310413);广东省自然科学基金(2016A050502004);广东省自然科学基金(2017A030312005);广东省自然科学基金(2017A030310029)

Copper-doped zinc sulfide nanoframes with three-dimensional photocatalytic surfaces for enhanced solar driven H₂ production

Junmin Huang, Jianmin Chen, Wangxi Liu, Jingwen Zhang, Junying Chen^*(), Yingwei Li^#()

State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China

Received:2021-04-17 Revised:2021-04-17 Online:2022-03-18 Published:2022-02-18
Contact: Junying Chen, Yingwei Li
Supported by:
National Natural Science Foundation of China(21825802);National Natural Science Foundation of China(21706078);Fundamental Research Funds for the Central Universities(2019PY11);Fundamental Research Funds for the Central Universities(2019MS038);Science and Technology Program of Guangzhou(201804020009);Pearl River S&T Nova Program of Guangzhou(201906010001);Guangdong Natural Science Foundation(2016A030310413);Guangdong Natural Science Foundation(2016A050502004);Guangdong Natural Science Foundation(2017A030312005);Guangdong Natural Science Foundation(2017A030310029)

摘要/Abstract

摘要：

太阳能转化为化学能被认为是当前能源和环境危机最具潜力的解决方案之一, 但在设计和制备高效的、可持续的半导体光催化剂方面仍需研究者不懈努力. 对半导体的组成、形貌进行重塑改性以提高光催化效率依然具有挑战性. 本文通过结合替位掺杂、酸性环境化学刻蚀和硫化三步策略制备了Cu掺杂的ZnS纳米框架材料, 旨在提高太阳能光催化产氢反应中的光利用率和电荷分离/迁移效率. 在制备过程中, Cu掺杂的ZIF-8菱形十二面体通过各向异性化学刻蚀转变为具有三维光催化活性表面的中空Cu-ZIF-8纳米框架, 进一步硫化转换为Cu掺杂ZnS(Cu-ZnS)纳米框架材料. 通过调控Cu-ZIF-8中Cu的掺杂量, 制备了一系列x%Cu-ZnS材料(x代表Cu²⁺/Zn²⁺的摩尔比, 分别为0, 0.5, 1, 2.5和5), 并考察了其在模拟太阳光激发下的光解水产氢性能.
通过对合成的x%Cu-ZnS纳米框架材料进行X射线衍射、扫描电子显微镜、透射电子显微镜以及X射线光电子能谱表征结果表明, Cu²⁺离子已成功地掺杂到ZnS纳米框架的晶格中. 在模拟太阳光照射下, Cu-ZnS纳米框架材料的光催化性能比纯ZnS和具有其他不同形貌的Cu-ZnS材料大幅提升. Cu的掺杂量对于调整Cu-ZnS的电子结构非常重要, 有助于增加光响应范围和改善电荷迁移效率. 在不同Cu/Zn摩尔比的x%Cu-ZnS中, 1%Cu-ZnS纳米框架材料具有最高的产氢性能, 在无助催化剂的条件下其光催化性能可达8.30 mmol h^-1g^-1. Cu-ZnS纳米材料因其独特的空心框架结构表现出反应物分子的三维可及性、较多的光催化活性位点、较大比表面积、较高电荷迁移率和较短的电荷迁移距离等优异特性. 因此, 在相同反应条件下, 1%Cu-ZnS纳米框架材料的光催化性能较大幅优于块状1%Cu-ZnS材料和空心1%Cu-ZnS材料. 1%Cu-ZnS纳米框架材料还具有优异的光解水产氢循环稳定性, 对循环25 h反应后样品进行X射线衍射和扫描电子显微镜表征, 表明其晶体结构和形貌结构未发生明显改变. 紫外漫反射、瞬态光电流响应、时间分辨荧光光谱和电化学交流阻抗等表征结果表明, Cu-ZnS纳米框架材料能够有效地将光吸收范围拓展到可见光甚至红外区域, 并能够有效促进光生电子/空穴的分离和迁移.
本文认为Cu-ZnS纳米框架材料光催化性能的大幅提升主要是由于其具备较好的Cu掺杂量、较大的比表面和开放的框架结构, 使其具有更多的反应活性位点、更高效的光生电荷的分离和迁移率和更高的光利用率. 综上, 本文制备的Cu-ZnS纳米框架结构策略可为设计具有独特形貌结构和组分的半导体光催化剂提供一定的借鉴.

关键词: 金属有机骨架, 太阳能-化学能能量转换, 金属硫化物, 产氢, 光催化

Abstract:

Solar-to-chemical energy conversion is perceived as one of the most potential solutions to the current energy and environmental crisis, yet requires major scientific endeavors on the development of efficient and sustainable photocatalysts. Remolding the composition and morphology of a semiconductor jointly for the purpose of improving photocatalysis efficiency remains challenging. Herein, we rationally fabricated Cu-doped ZnS nanoframes via a simple conjunct strategy of substitutional doping, chemical acidic etching, and sulfidation, aiming at enhancing the light utilization and charge separation/transfer efficiency for solar-light-driven hydrogen generation. Cu-doped zeolitic imidazolate framework-8 (ZIF-8) rhombic dodecahedrons are transformed to hollow Cu-ZIF-8 nanoframes converted to Cu-ZnS nanoframes with three-dimensional photocatalytic active surfaces via anisotropic chemical etching, which is further converted to Cu-ZnS nanoframes. By combining the merits of optimal heteroatom doping and frame-like open architecture, the obtained 1%Cu-doped ZnS nanoframe exhibits high photocatalytic activity under solar light irradiation with improved hydrogen production rate up to 8.30 mmol h^-1g^-1 and excellent stability in the absence of cocatalysts, which is significantly improved in comparison with those of the bare ZnS and Cu-ZnS with different morphologies. This work inspired by merging the merits of metal doping and anisotropic chemical etching may shed light on the rational design and fabrication of advanced photocatalysts.

Key words: Metal-organic frameworks, Solar-to-chemical energy conversion, Metal sulfides, Hydrogen production, Photocatalysis

黄俊敏, 陈健民, 刘望喜, 张静文, 陈俊英, 李映伟. 具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢[J]. 催化学报, 2022, 43(3): 782-792.

Junmin Huang, Jianmin Chen, Wangxi Liu, Jingwen Zhang, Junying Chen, Yingwei Li. Copper-doped zinc sulfide nanoframes with three-dimensional photocatalytic surfaces for enhanced solar driven H₂ production[J]. Chinese Journal of Catalysis, 2022, 43(3): 782-792.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63864-0

https://www.cjcatal.com/CN/Y2022/V43/I3/782

图/表 8

Scheme 1. Schematic illustration of the synthesis process of Cu-ZIF-8 nanoframe.

Fig. 2. (a) PXRD patterns of the x%Cu-ZnS nanoframes. (b) The corresponding magnified PXRD patterns in the region of 20° to 40°.

Fig. 1. FESEM (a,b) and TEM (c) images of 1%Cu-ZIF-8 nanoframe. FESEM (d,e), TEM (f), HRTEM (g), HAADF-STEM (h) and elemental mapping (i-l) images of 1%Cu-ZnS nanoframe.

Fig. 3. The survey spectra (a) and high-resolution XPS spectra of S 2p (b), Zn 2p (c), and Cu 2p (d) of the x%Cu-ZnS nanoframes.

Fig. 4. (a) Photocatalytic hydrogen evolution curves of x%Cu-ZnS nanoframes; (b) Photocatalytic hydrogen production in five consecutive cycles for 1%Cu-ZnS nanoframe under simulated solar light irradiation; (c) Photocatalytic hydrogen evolution curves of different samples.

Fig. 5. UV-Vis DRS (a), Steady-state PL (b), EIS Nyquist plots (c), and transient photocurrent responses (d) of the x%Cu-ZnS nanoframes.

Fig. 6. UV-Vis DRS (a), time-resolved PL decay profiles (b), EIS Nyquist plots (c), and transient photocurrent responses (d) of bulk, hollow, and nanoframe-structural 1%Cu-ZnS.

Fig. 7. Schematic illustration of the photoexcited charge carrier migration and hydrogen generation over the 1% Cu-doped ZnS nanoframe.

参考文献

[1]	M. Jakob, J. Hilaire, Nature, 2015, 517, 150-151.
[2]	B. Zhu, R. Zou, Q. Xu, Adv. Energy Mater., 2018, 8, 1801193.
[3]	J. Chen, K. Shen, Y. Li, ChemSusChem, 2017, 10, 3165-3187.
[4]	D. K. Sun, J. W. Shi, D. D. Ma. Y, J. Zou, G. T. Sun, S. M. Mao, L. W. Sun, Y. H. Cheng, Chin. J. Catal., 2021, 41, 1421-1429.
[5]	Q. Wang, K. Domen, Chem. Rev., 2020, 120, 919-985.
[6]	Y. Tachibana, L. Vayssieres, J. R. Durrant, Nat. Photonics, 2012, 6, 511-518.
[7]	T. Chen, L. Z. Liu, C. Hu, H. W. Huang, Chin. J. Catal., 2021, 42, 1413-1438.
[8]	P. Zhang, X. W. Lou, Adv. Mater., 2019, 31, 1900281.
[9]	S. Ye, C. Ding, M. Liu, A. Wang, Q. Huang, C. Li, Adv. Mater., 2019, 31, 1902069.
[10]	X. -B. Li, Z.-K. Xin, S.-G. Xia, X.-Y. Gao, C.-H. Tung, L.-Z. Wu, Chem. Soc. Rev., 2020, 49, 9028-9056.
[11]	F. Wen, C. Li, Acc. Chem. Res., 2013, 46, 2355-2364.
[12]	X. Li, J. Yu, J. Low, Y. Fang, J. Xiao, X. Chen, J. Mater. Chem. A, 2015, 3, 2485-2534.
[13]	X. Li, J. Yu, M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603-2636.
[14]	S. C. Warren, K. Voïtchovsky, H. Dotan, C. M. Leroy, M. Cornuz, F. Stellacci, C. Hébert, A.Rothschild, M. Grätzel, Nat. Mater., 2013, 12, 842-849.
[15]	T. Yao, X. An, H. Han, J. Q. Chen, C. Li, Adv. Energy Mater., 2018, 8, 1800210.
[16]	S. Huang, T. Ouyang, B. Zheng, M. Dan, Z. Liu, Angew. Chem. Int. Ed., 2021, 60, 9546-9552.
[17]	S. Chandrasekaran, L. Yao, L. Deng, C. Bowen, Y. Zhang, S. Chen, Z. Lin, F. Peng, P. Zhang, Chem. Soc. Rev., 2019, 48, 4178-4280.
[18]	R. Wei, Z. Huang, G. Gu, Z. Wang, L. Zeng, Y. Chen, Z. Liu, Appl. Catal. B, 2018, 231, 101-107.
[19]	J. Zhou, J. Zhao, R. Liu, Appl. Catal. B, 2020, 278, 119265.
[20]	J. Lee, S. Ham, D. Choi, D.-J. Jang, Nanoscale, 2018, 10, 14254-14263.
[21]	Y. Hong, J. Zhang, F. Huang, J. Zhang, X. Wang, Z. Wu, Z. Lin, J. Yu, J. Mater. Chem. A, 2015, 3, 13913-13919.
[22]	J. Chen, J. Chen, Y. Li, J. Mater. Chem. A, 2017, 5, 24116-24125.
[23]	X. Y. Yu, X. W. Lou, Adv. Energy Mater., 2018, 8, 1701592.
[24]	P. Wang, Z. Shen, Y. Xia, H. Wang, L. Zheng, W. Xi, S. Zhan, Adv. Funct. Mater., 2019, 29, 1807013.
[25]	G. J. Lee, S. Anandan, S. J. Masten, J. J. Wu, Renewable Energy, 2016, 89, 18-26.
[26]	A. Kudo, M. Sekizawa, Chem. Commun., 2000, 1371-1372.
[27]	W. Yang, L. Zhang, J. Xie, X. Zhang, Q. Liu, T. Yao, S. Wei, Q. Zhang, Y. Xie, Angew. Chem., Int. Ed., 2016, 55, 6716-6720.
[28]	X. Y. Yu, L. Yu, H. B. Wu, X. W. Lou, Angew. Chem. Int. Ed., 2015, 54, 5331-5335.
[29]	J. R. Greer, Science, 2014, 343, 1319.
[30]	T. Kwon, M. Jun, K. Lee, Adv. Mater., 2020, 32, 2001345.
[31]	J. Zhang, H. Hu, Z. Li, X. W. Lou, Angew. Chem. Int. Ed., 2016, 55, 3982-3986.
[32]	S. Wang, Y. Wang, S. L. Zhang, S.-Q. Zang, X. W. Lou, Adv. Mater., 2019, 31, 1970291.
[33]	J. Chen, Z. Shen, S. Lv, K. Shen, R. Wu, X.-F. Jiang, T. Fan, J. Chen, Y. Li, J. Mater. Chem. A, 2018, 6, 19631-19642.
[34]	S. Huang, B. Zheng, Z. Tang, X. Mai, T. Ouyang, Z. Liu, Chem. Eng. J., 2021, 422, 130086.
[35]	Y. Huang, Y. Fang, X. F. Lu, D. Luan, X. W. Lou, Angew. Chem. Int. Ed., 2020, 59, 19914-19918.
[36]	Y. Fang, D. Luan, Y. Chen, S. Gao, X. W. Lou, Angew. Chem. Int. Ed., 2020, 59, 2644-2648.
[37]	J. Park, Y. J. Sa, H. Baik, T. Kwon, S. H. Joo, K. Lee, ACS Nano, 2017, 11, 5500-5509.
[38]	Y. Liu, D. Huang, M. Cheng, Z. Liu, C. Lai, C. Zhang, C. Zhou, W. Xiong, L. Qin, B. Shao, Q. Liang, Coord. Chem. Rev., 2020, 409, 213220.
[39]	Q. Y. Chen, S. J. Li, H. Y. Xu, G. F. Wang, Y. Qu, P. F. Zhu, D. S. Wang, Chin. J. Catal., 2020, 41, 514-523.
[40]	W. Sun, X. Tao, P. Du, Y. Wang, Chem. Eng. J., 2019, 366, 622-630.
[41]	Q. Liang, J. Chen, F. Wang, Y. Li, Coord. Chem. Rev., 2020, 424, 213488.
[42]	Y. Xu, K. L. Ren, R. Xu, Chin. J. Catal., 2021, 42, 1370-1378.
[43]	J. Liu, D. Zhu, C. Guo, A. Vasileff, S.-Z. Qiao, Adv. Energy Mater., 2017, 7, 1700518.
[44]	Y. Wang, S. Wang, S. L. Zhang, X. W. Lou, Angew. Chem. Int. Ed., 2020, 59, 11918-11922.
[45]	S. Jeoung, I. T. Ju, J. H. Kim, S. H. Joo, H. R. Moon, J. Mater. Chem. A, 2018, 6, 18906-18911.
[46]	Q. Lai, J. Zhu, Y. Zhao, Y. Liang, J. He, J. Chen, Small, 2017, 13, 1700740.
[47]	C. Avci, J. Arinez-Soriano, A. Carne-Sanchez, V. Guillerm, C. Carbonell, I. Imaz, D. Maspoch, Angew. Chem. Int. Ed., 2015, 54, 14417-14421.
[48]	W. Wang, G.-J. Lee, P. Wang, Z. Qiao, N. Liu, J. J. Wu, Sep. Purif. Technol., 2020, 237, 116469.
[49]	B. B. Srivastava, S. Jana, N. Pradhan, J. Am. Chem. Soc., 2011, 133, 1007-1015.
[50]	Y. Fang, X.-Y. Yu, X. W. Lou, Adv. Mater., 2018, 30, 1706668.
[51]	M. Zhang, J. Zhang, Z. Zhou, S. Chen, T. Zhang, F. Song, Q. Zhang, N. Tsubaki, Y. Tan, Y. Han, Appl. Catal. B, 2020, 264, 118522.
[52]	R. Rameshbabu, P. Ravi, M. Sathish, Chem. Eng. J., 2019, 360, 1277-1286.
[53]	D. Jiang, Z. Sun, H. Jia, D. Lu, P. Du, J. Mater. Chem. A, 2016, 4, 675-683.
[54]	Q. Mao, J. Chen, H. Chen, Z. Chen, J. Chen, Y. Li, J. Mater. Chem. A, 2019, 7, 8472-8484.
[55]	J. Zhang, J. Yu, Y. Zhang, Q. Li, J. R. Gong, Nano Lett., 2011, 11, 4774-4779.
[56]	Y. Li, G. Chen, Q. Wang, X. Wang, A. Zhou, Z. Shen, Adv. Funct. Mater., 2010, 20, 3390-3398.
[57]	X. Shi, L. Mao, C. Dai, P. Yang, J. Zhang, F. Dong, L. Zheng, M. Fujitsuka, H. Zheng, J. Mater. Chem. A, 2020, 8, 13376-13384.
[58]	Y. Wang, J. Wu, J. Zheng, R. Jiang, R. Xu, Catal. Sci. Technol., 2012, 2, 581-588.
[59]	R. Chauhan, A. Kumar, R. P. Chaudhary, J. Lumin., 2014, 145, 6-12.
[60]	J. Yao, J. Chen, K. Shen, Y. Li, J. Mater. Chem. A, 2018, 6, 3571-3582.
[61]	W. Liu, Y. Shang, A. Zhu, P. Tan, Y. Liu, L. Qiao, D. Chu, X. Xiong, J. Pan, J. Mater. Chem. A, 2017, 5, 12542-12549.

具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢

Copper-doped zinc sulfide nanoframes with three-dimensional photocatalytic surfaces for enhanced solar driven H₂ production

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 8

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[5]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[6]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[7]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[8]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[9]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[10]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[11]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[12]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[13]	乔秀清, 李晨, 王紫昭, 侯东芳, 李东升. TiO_2-_x@C/MoO₂肖特基结: 合理设计及高效电荷分离提升光催化性能[J]. 催化学报, 2023, 51(8): 66-79.
[14]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.
[15]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.

具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢

Copper-doped zinc sulfide nanoframes with three-dimensional photocatalytic surfaces for enhanced solar driven H2 production

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 8

参考文献

相关文章 15

编辑推荐

Metrics

Copper-doped zinc sulfide nanoframes with three-dimensional photocatalytic surfaces for enhanced solar driven H₂ production