金属-有机骨架衍生的Ni-CNT/ZnIn2S4异质结用于光催化产氢及其电荷转移途径的确定

doi:10.3866/PKU.WHXB202304018

物理化学学报 >> 2024, Vol. 40 >> Issue (1): 2304018.doi: 10.3866/PKU.WHXB202304018

论文上一篇

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

赖可溱¹^,², 李丰彦¹^,², 李宁¹^,², 高旸钦¹^,², 戈磊¹^,²^,*()

¹ 中国石油大学(北京)新能源与材料学院重质油国家重点实验室, 北京 102249
² 中国石油大学(北京)新能源与材料学院材料科学与工程系, 北京 102249

收稿日期:2023-04-06 录用日期:2023-05-22 发布日期:2023-08-21
通讯作者: 戈磊 E-mail:gelei@cup.edu.cn
基金资助:
国家重点研发计划(2021YFA1501300);国家重点研发计划(2019YFC1907602);国家自然科学基金(51572295);国家自然科学基金(21273285);国家自然科学基金(21003157)

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution

Kezhen Lai¹^,², Fengyan Li¹^,², Ning Li¹^,², Yangqin Gao¹^,², Lei Ge¹^,²^,*()

¹ State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China
² Department of Materials Science and Engineering, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China

Received:2023-04-06 Accepted:2023-05-22 Published:2023-08-21
Contact: Lei Ge E-mail:gelei@cup.edu.cn
Supported by:
the National Key R & D Program of China(2021YFA1501300);the National Key R & D Program of China(2019YFC1907602);National Natural Science Foundation of China(51572295);National Natural Science Foundation of China(21273285);National Natural Science Foundation of China(21003157)

摘要/Abstract

摘要：

氢气是缓解环境污染和能源短缺的零污染绿色能源，利用太阳能诱导半导体裂解水制氢是最环保的方法之一。本文以MOFs衍生的Ni-CNT(Ni修饰的碳纳米管)作为非贵金属助催化剂，通过简单的油浴法原位生长ZnIn₂S₄纳米片合成了Ni-CNT/ZnIn₂S₄。在Ni-CNT/ZnIn₂S₄中，Ni纳米颗粒包裹在CNT的顶部和横截面上，有效地阻止了Ni纳米颗粒的团聚。Ni-CNT/ZnIn₂S₄异质结构具有紧密的接触界面，有利于电荷转移，可作为高效的析氢光催化剂。38Ni-CNT/ZnIn₂S₄样品具有最佳的产氢性能(12267 μmol·h⁻¹·g⁻¹)，约为纯ZnIn₂S₄的6.4倍，且在420 nm单色光下其表观量子效率达到11.3%。X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)结果证实了Ni-CNT/ZnIn₂S₄异质结构的存在。电化学测试表明，Ni-CNT与ZnIn₂S₄的结合促进了光生电荷的转移，有效地阻止了光生载流子的快速复合，从而增强了ZnIn₂S₄的析氢性能。电子自旋共振(ESR)结果进一步证明了Ni-CNT助催化剂的存在延长了ZnIn₂S₄光生电荷的寿命，促进了光生电荷和空穴的分离效率。通过密度泛函理论计算探索并确定了异质结界面中的电荷转移途径。Ni、CNT和ZnIn₂S₄费米能级的差异导致界面处电荷发生迁移从而形成内嵌电场，ZnIn₂S₄的能带向下弯曲，促进光生电子从ZnIn₂S₄流向Ni-CNT电子受体。平面平均电子密度差结果证实了热电子从Ni转移至CNT再转移至ZnIn₂S₄，表明光生电子转移途径为ZnIn₂S₄ → CNT → Ni。此外，吸附H*吉布斯自由能(ΔG_H*)和晶体轨道哈密顿布居(COHP)结果表明Ni纳米颗粒可作为析氢反应的活性位点，促进了产氢效率。本工作将为开发低成本、高效的非贵金属光催化制氢催化剂提供新的策略。

关键词: Ni-CNT, 光催化, 析氢, ZnIn₂S₄, 助催化剂

Abstract:

Hydrogen is an important zero-pollution green energy source with potential for alleviating environmental contamination and energy shortages. Hydrogen evolution via solar-energy-induced semiconducting water splitting is among the most environmentally friendly methods available to date. In this study, a metal–organic-framework-derived, Ni-decorated carbon nanotube (Ni-CNT) is used as a non-noble co-catalyst. This Ni-CNT is grown in situ on ZnIn₂S₄ nanosheets using a simple one-step oil bath strategy, wherein Ni nanoparticles are wrapped around the top and cross sections of the nanotubes, preventing their agglomeration. Notably, Ni-CNT/ZnIn₂S₄ heterostructures feature intimate contact interfaces that promote charge transfer, facilitating their use as efficient photocatalysts for hydrogen evolution. The 38Ni-CNT/ZnIn₂S₄ sample exhibits a high H₂ production rate (12267 μmol·h⁻¹·g⁻¹), with an apparent quantum efficiency (AQE) of 11.3% under 420 nm monochromatic light irradiation, which is nearly 6.4 times that of pure ZnIn₂S₄. The results of X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) corroborate the observations on Ni-CNT/ZnIn₂S₄ heterostructures. Electrochemical measurements reveal that the combination of the Ni-CNT and ZnIn₂S₄ facilitates the transfer of photogenerated electrons and effectively prevents rapid recombination of photocarriers, thus improving the hydrogen evolution performance of ZnIn₂S₄. Electron spin resonance (ESR) results further prove that co-catalyst Ni-CNTs are beneficial for prolonging the lifetimes of ZnIn₂S₄ photogenerated electrons, thereby achieving effective charge separation. A charge transfer pathway in the heterojunction interfaces is further explored and confirmed by density functional theory (DFT) calculations. The difference in the Fermi level energy (E_f) contributes to both charge migration and the generation of a built-in electronic field (BEF), indicating that the energy band of ZnIn₂S₄ bends downward, which is favorable for photogenerated electron flow from ZnIn₂S₄ to the Ni-CNT electron acceptor. The results of planar-averaged electron density difference analysis confirm that the hot electrons are transferred from Ni nanoparticles to the CNT and then to the ZnIn₂S₄ nanosheets, indicating the formation of a photogenerated electron transfer pathway of ZnIn₂S₄ → CNT → Ni. Furthermore, Gibbs free energy of H* adsorption (ΔG_H*) and crystal orbital Hamilton population (COHP) analysis indicate that Ni nanoparticles can serve as active sites, promoting H₂ evolution. Thus, the present study formulates a new strategy for developing low-cost, high-efficiency, non-noble-metal co-catalysts for photocatalytic hydrogen production.

Key words: Ni-CNT, Photocatalysis, H₂ evolution, ZnIn₂S₄, Co-catalysts

赖可溱, 李丰彦, 李宁, 高旸钦, 戈磊. 金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定[J]. 物理化学学报, 2024, 40(1), 2304018. doi: 10.3866/PKU.WHXB202304018

Kezhen Lai, Fengyan Li, Ning Li, Yangqin Gao, Lei Ge. Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution[J]. Acta Phys. -Chim. Sin. 2024, 40(1), 2304018. doi: 10.3866/PKU.WHXB202304018

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202304018

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I1/2304018

图/表 9

Scheme 1

Fig 1

Fig 2

Fig 3

Table 1

Fig 4

Fig 5

Fig 6

Scheme 2

参考文献 52

1	Turner J. A. Science 2004, 305, 972. doi: 10.1126/science.1103197
2	Li Y. ; Zhang H. ; Xu T. ; Lu Z. ; Wu X. ; Wan P. ; Sun X. ; Jiang L. Adv. Funct. Mater. 2015, 25, 1737. doi: 10.1002/adfm.201404250
3	Abe J. O. ; Popoola A. P. I. ; Ajenifuja E. ; Popoola O. M. Int. J. Hydrog. Energy 2019, 44, 15072. doi: 10.1016/j.ijhydene.2019.04.068
4	Armaroli N. ; Balzani V. ChemSusChem 2011, 4, 21. doi: 10.1002/cssc.201000182
5	Ball M. ; Wietschel M. Int. J. Hydrog. Energy 2009, 34, 615. doi: 10.1016/j.ijhydene.2008.11.014
6	Fujishima A. ; Honda K. Nature 1972, 238, 37. doi: 10.1038/238037a0
7	Hashimoto K. ; Irie H. ; Fujishima A. Jpn. J. Appl. Phys. 2005, 44, 8269. doi: 10.1143/JJAP.44.8269
8	Li X. L. ; Yang G. Q. ; Li S. S. ; Xiao N. ; Li N. ; Gao Y. Q. ; Lv D. ; Ge L. Chem. Eng. J. 2020, 379, 122350. doi: 10.1016/j.cej.2019.122350
9	Li X. L. ; He R. B. ; Dai Y. J. ; Li S. S. ; Xiao N. ; Wang A. X. ; Gao Y. Q. ; Li N. ; Gao J. F. ; Zhang L. H. ; et al Chem. Eng. J. 2020, 400, 125474. doi: 10.1016/j.cej.2020.125474
10	Zhang Y. ; Yun S. ; Sun M. ; Wang X. ; Zhang L. ; Dang J. ; Yang C. ; Yang J. ; Dang C. ; Yuan S. J. Colloid Interface Sci. 2021, 604, 441. doi: 10.1016/j.jcis.2021.06.152
11	Cao S. ; Yu J. ; Wageh S. ; Al-Ghamdi A. A. ; Mousavi M. ; Ghasemi J. B. ; Xu F. J. Mater. Chem. A 2022, 10, 17174. doi: 10.1039/D2TA05181H
12	Wang L. ; Yang T. ; Peng L. ; Zhang Q. ; She X. ; Tang H. ; Liu Q. Chin. J. Catal. 2022, 43, 2720. doi: 10.1016/S1872-2067(22)64133-0
13	Gou X. ; Cheng F. ; Shi Y. ; Zhang L. ; Peng S. ; Chen J. ; Shen P. J. Am. Chem. Soc. 2006, 128, 7222. doi: 10.1021/ja0580845
14	Bai J. ; Chen W. ; Shen R. ; Jiang Z. ; Zhang P. ; Liu W. ; Li X. J. Mater. Sci. Technol. 2022, 112, 85. doi: 10.1016/j.jmst.2021.11.003
15	Gao B. ; Chen W. ; Liu J. ; An J. ; Wang L. ; Zhu Y. ; Sillanpää M. J. Photochem. Photobiol. A 2018, 364, 732. doi: 10.1016/j.jphotochem.2018.07.008
16	Song Y. ; Zhang J. ; Dong X. ; Li H. Energy Technol. 2021, 9 (5), 2100033. doi: 10.1002/ente.202100033
17	Peng S. ; Wu Y. ; Zhu P. ; Thavasi V. ; Ramakrishna S. ; Mhaisalkar S. G. J. Mater. Chem. 2011, 21, 15718. doi: 10.1039/C1JM12432C
18	Sun L. ; Qi Y. ; Jia C. J. ; Jin Z. ; Fan W. Nanoscale 2014, 6, 2649. doi: 10.1039/C3NR06104C
19	Zhou P. ; Zhang Q. ; Xu Z. ; Shang Q. ; Wang L. ; Chao Y. ; Li Y. ; Chen H. ; Lv F. ; Zhang Q. ; et al Adv. Mater. 2020, 32 (7), 1904249. doi: 10.1002/adma.201904249
20	Xiao N. ; Li S. ; Li X. ; Ge L. ; Gao Y. ; Li N. Chin. J. Catal. 2020, 41, 642. doi: 10.1016/S1872-2067(19)63469-8
21	Ha Y. ; Shi L. ; Yan X. ; Chen Z. ; Li Y. ; Xu W. ; Wu R. ACS Appl. Mater. Interfaces 2019, 11, 45546. doi: 10.1021/acsami.9b13580
22	Luo S. ; Li X. ; Zhang B. ; Luo Z. ; Luo M. ACS Appl. Mater. Interfaces 2019, 11, 26891. doi: 10.1021/acsami.9b07100
23	Jiang J. ; Liu Q. ; Zeng C. ; Ai L. J. Mater. Chem. A 2017, 5, 16929. doi: 10.1039/C7TA04893
24	Zhao H. ; Yuan Z.-Y. Catal. Sci. Technol. 2017, 7, 330. doi: 10.1039/C6CY01719C
25	Li X. ; Gao Y. ; Li N. ; Ge L. Int. J. Hydrog. Energy 2022, 47, 27961. doi: 10.1016/j.ijhydene.2022.06.119
26	Guo Y. ; Tang J. ; Wang Z. ; Kang Y.-M. ; Bando Y. ; Yamauchi Y. Nano Energy 2018, 47, 494. doi: 10.1016/j.nanoen.2018.03.012
27	Zeng Z. ; Su Y. ; Quan X. ; Choi W. ; Zhang G. ; Liu N. ; Kim B. ; Chen S. ; Yu H. ; Zhang S. Nano Energy 2020, 69, 104409. doi: 10.1016/j.nanoen.2019.104409
28	Jiang K. ; Siahrostami S. ; Zheng T. ; Hu Y. ; Hwang S. ; Stavitski E. ; Peng Y. ; Dynes J. ; Gangisetty M. ; Su D. ; et al Energy Environ. Sci. 2018, 11, 893. doi: 10.1039/C7EE03245E
29	Gao J. ; Zhang F. ; Xue H. ; Zhang L. ; Peng Y. ; Li X. ; Gao Y. ; Li N. ; Lei G. Appl. Catal. B 2021, 281, 119509. doi: 10.1016/j.apcatb.2020.119509
30	Sun Z. ; Wang Y. ; Zhang L. ; Wu H. ; Jin Y. ; Li Y. ; Shi Y. ; Zhu T. ; Mao H. ; Liu J. ; et al Adv. Funct. Mater. 2020, 30 (15), 1910482. doi: 10.1002/adfm.201910482
31	Yu H. ; Fisher A. ; Cheng D. ; Cao D. ACS Appl. Mater. Interfaces 2016, 8, 21431. doi: 10.1021/acsami.6b04189
32	Chen Z. ; Wu R. ; Liu Y. ; Ha Y. ; Guo Y. ; Sun D. ; Liu M. ; Fang F. Adv. Mater. 2018, 30 (30), 1802011. doi: 10.1002/adma.201802011
33	Joya K. S. ; Sinatra L. ; AbdulHalim L. G. ; Joshi C. P. ; Hedhili M. N. ; Bakr O. M. ; Hussain I. Nanoscale 2016, 8, 9695. doi: 10.1039/C6NR00709K
34	Yang L. ; Shi L. ; Wang D. ; Lv Y. ; Cao D. Nano Energy 2018, 50, 691. doi: 10.1016/j.nanoen.2018.06.023
35	Zou H. ; Li G. ; Duan L. ; Kou Z. ; Wang J. Appl. Catal. B 2019, 259, 118100. doi: 10.1016/j.apcatb.2019.118100
36	Shen R. C. ; Hao L. ; Chen Q. ; Zheng Q. Q. ; Zhang P. ; Li X. Acta Phys. -Chim. Sin. 2022, 38 (7), 2110014.
	沈荣晨; 郝磊; 陈晴; 郑巧清; 张鹏; 李鑫; 物理化学学报, 2022, 38 (7), 2110014. doi: 10.3866/PKU.WHXB202110014
37	Li S. ; Gao Y. ; Li N. ; Ge L. ; Bu X. ; Feng P. Energy Environ. Sci. 2021, 14, 1897. doi: 10.1039/D0EE03697H
38	Lu Z. ; Wang J. ; Huang S. ; Hou Y. ; Li Y. ; Zhao Y. ; Mu S. ; Zhang J. ; Zhao Y. Nano Energy 2017, 42, 334. doi: 10.1016/j.nanoen.2017.11.004
39	Sun M. ; Li Z. ; Liu Y. ; Guo D. ; Xie Z. ; Huang Q. Int. J. Hydrog. Energy 2020, 45, 31892. doi: 10.1016/j.ijhydene.2020.08.213
40	Di T. ; Zhang L. ; Cheng B. ; Yu J. ; Fan J. J. Mater. Sci. Technol. 2020, 56, 170. doi: 10.1016/j.jmst.2020.03.032
41	Xie Y. ; Feng C. ; Guo Y. ; Li S. ; Guo C. ; Zhang Y. ; Wang J. Appl. Surf. Sci. 2021, 536, 147786. doi: 10.1016/j.apsusc.2020.147786
42	Wu K. ; Wu C. ; Bai W. ; Li N. ; Gao Y. ; Ge L. Colloids Surf. A 2023, 663, 131089. doi: 10.1016/j.colsurfa.2023.131089
43	Li X. ; Song S. ; Gao Y. ; Ge L. ; Song W. ; Ma T. ; Liu J. Small 2021, 17 (31), 2101315. doi: 10.1002/smll.202101315
44	Lu P. ; Yang Y. ; Yao J. ; Wang M. ; Dipazir S. ; Yuan M. ; Zhang J. ; Wang X. ; Xie Z. ; Zhang G. Appl. Catal. B 2019, 241, 113. doi: 10.1016/j.apcatb.2018.09.025
45	Liu H. ; Zhang J. ; Ao D. Appl. Catal. B 2018, 221, 433. doi: 10.1016/j.apcatb.2017.09.043
46	Zhu Y. ; Chen J. ; Shao L. ; Xia X. ; Liu Y. ; Wang L. Appl. Catal. B 2020, 268, 118744. doi: 10.1016/j.apcatb.2020.118744
47	Zhang Y. N. ; Gao M. ; Chen S. T. ; Wang H. Q. ; Huo P. W. Acta Phys. -Chim. Sin. 2023, 39 (6), 2211051.
	张怡宁; 高明; 陈松涛; 王会琴; 霍鹏伟; 物理化学学报, 2023, 39 (6), 2211051. doi: 10.3866/PKU.WHXB202211051
48	Wang S. ; Wang Y. ; Zhang S. L. ; Zang S. Q. ; Lou X. W. Adv. Mater. 2019, 31 (41), 1903404. doi: 10.1002/adma.201903404
49	Li Z. ; He H. ; Cao H. ; Sun S. ; Diao W. ; Gao D. ; Lu P. ; Zhang S. ; Guo Z. ; Li M. ; et al Appl. Catal. B 2019, 240, 112. doi: 10.1016/j.apcatb.2018.08.074
50	Li T. ; Luo G. ; Liu K. ; Li X. ; Sun D. ; Xu L. ; Li Y. ; Tang Y. Adv. Funct. Mater. 2018, 28 (51), 1805828. doi: 10.1002/adfm.201805828
51	Liu C. ; Yang Z. ; Li Y. RSC Adv. 2016, 6, 32983. doi: 10.1039/C6RA00984K
52	Tang J. Y. ; Yang D. ; Zhou W. G. ; Guo R. T. ; Pan W. G. ; Huang C. Y. J. Catal. 2019, 370, 79. doi: 10.1016/j.jcat.2018.12.009

Sample	H₂ evolution (μmol∙h⁻¹∙g⁻¹)	AQY (%)	Reference
WO₃@ZnIn₂S₄	8500	3.61	10
ZnIn₂S₄/g-C₃N₄/Ti₃C₂	2452.1	11.9	11
Ti₃C₂/ZnIn₂S₄/CdS	8930	0.79	12
g-C₃N₄/ZnIn₂S₄	2780	7.05	14
ZnIn₂S₄/NH₂-MIL-125(Ti)	2204.2	4.3	45
ZnIn₂S₄/CdS	3072	15.9	46
Ni-CNT/ZnIn₂S₄	12267	11.3	this work

[1]	秦春玲, 陈爽, Hassanien Gomaa, Mohamed A. Shenashen, Sherif A. El-Safty, 刘倩, 安翠华, 刘熙俊, 邓齐波, 胡宁. 外加物理场调控二维材料的HER和OER性能[J]. 物理化学学报, 2024, 40(9): 2307059 - .
[2]	蔡宇珊, 肖方兴. MXenes基光催化剂的进展、挑战和展望[J]. 物理化学学报, 2024, 40(8): 2306048 - .
[3]	孙巍, 王永靖, 项坤, 白赛帅, 王海涛, 邹菁, Arramel, 江吉周. CoP修饰Ti₃C₂T_x MXene纳米复合材料作为高效析氢反应电催化剂[J]. 物理化学学报, 2024, 40(8): 2308015 - .
[4]	肖林锋, 任婉璐, 沈诗诗, 陈梦姗, 廖润华, 周英棠, 李喜宝. 调控ZnIn₂S₄/Bi₂O₃ S型异质结的电子结构和润湿性增强光催化析氢[J]. 物理化学学报, 2024, 40(8): 2308036 - .
[5]	王海涛, 余良浪, 江吉周, Arramel, 邹菁. 硫取代氮增强g-C₃N₄光催化产氢性能[J]. 物理化学学报, 2024, 40(5): 2305047 - .
[6]	胡佳伟, 夏楷, 杨奥, 张志豪, 肖雯, 刘超, 张勤芳. 超薄2D/2D NiPS₃/C₃N₅异质结的界面工程促进光催化产氢[J]. 物理化学学报, 2024, 40(5): 2305043 - .
[7]	丁慧伟, 彭博, 王志豪, 韩巧凤. 铋基光催化剂的金属或非金属改性研究进展[J]. 物理化学学报, 2024, 40(4): 2305048 - .
[8]	陈慧滢, 朱浩林, 廖培钦, 陈小明. 一例整合了三联吡啶钌和卟啉锌的金属-有机框架材料用于光催化二氧化碳还原全反应[J]. 物理化学学报, 2024, 40(4): 2306046 - .
[9]	郭艳辉, 魏丽, 温中林, 戚朝荣, 江焕峰. 二氧化碳转化为氨基甲酸酯的研究进展[J]. 物理化学学报, 2024, 40(4): 2307004 - .
[10]	汪园青, 潘育松, 朱红梧, 向妍蕾, 韩蓉, 黄润, 杜超, 潘成岭. 高级氧化和可见光照射协同作用下Bi₂WO₆对有机污染物降解的催化活性增强[J]. 物理化学学报, 2024, 40(4): 2304050 - .
[11]	邢雅娟, 薛辉, 孙静, 郭念坤, 宋天山, 孙佳雯, 郝翊茹, 王勤. Cu₃P辅助诱导Ni₂P电荷定向转移和表面重构以获得高效析氧活性[J]. 物理化学学报, 2024, 40(3): 2304046 - .
[12]	卢华森, 宋世旭, 贾萁森, 刘光波, 姜鲁华. 用于光电催化水分解的氧化亚铜基光电阴极研究进展[J]. 物理化学学报, 2024, 40(2): 2304035 - .
[13]	方文诚, 刘东, 张莹, 冯浩, 李强. 多酸修饰的CuBi₂O₄/Mg-CuBi₂O₄同质结光阴极用于高效光电化学转化[J]. 物理化学学报, 2024, 40(2): 2304006 - .
[14]	曹玥晗, 郭瑞, 马敏智, 黄泽皑, 周莹. 活性位点电子密度变化对光催化CO₂活化和选择转化的影响[J]. 物理化学学报, 2024, 40(1): 2303029 - .
[15]	张珹博, 陶晓萍, 蒋文超, 郭俊雪, 张鹏飞, 李灿, 李仁贵. 微波辅助合成促进铬酸铋晶体的光生电荷分离[J]. 物理化学学报, 2024, 40(1): 2303034 - .

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution

RichHTML

PDF

赞