构建低成本的Ni3C/孪晶Zn0.5Cd0.5S异质结/同质结纳米杂化体系来实现高效的光催化分解水产氢

doi:10.1016/S1872-2067(20)63600-2

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 25-36.DOI: 10.1016/S1872-2067(20)63600-2

构建低成本的Ni₃C/孪晶Zn_0.5Cd_0.5S异质结/同质结纳米杂化体系来实现高效的光催化分解水产氢

沈荣晨^a, 丁英娜^b, 李世邦^b, 张鹏^c, 向全军^d, 吴永豪^e^,^#(), 李鑫^a^,^b^,^*()

^a华南农业大学林学与风景园林学院, 农业部能源植物资源与利用重点实验室, 广东广州510642
^b华南农业大学材料与能源学院, 广东广州510642
^c郑州大学材料与工程学院, 低碳环保材料智能设计国际联合研究中心, 河南郑州450001
^d电子科技大学电子薄膜与集成器件国家重点实验室, 四川成都610054
^e香港城市大学能源与环境学院, 香港

收稿日期:2020-03-02 接受日期:2020-04-21 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 吴永豪,李鑫
基金资助:
国家自然科学基金(21975084);国家自然科学基金(51672089);广东省重大科技研发计划(2017B020238005);武汉理工大学材料复合新技术国家重点实验室(2015-KF-7);香港研究资助局-优配研究金(GRF13054)

Constructing low-cost Ni₃C/twin-crystal Zn_0.5Cd_0.5S heterojunction/homojunction nanohybrids for efficient photocatalytic H₂ evolution

Rongchen Shen^a, Yingna Ding^b, Shibang Li^b, Peng Zhang^c, Quanjun Xiang^d, Yun Hau Ng^e^,^#(), Xin Li^a^,^b^,^*()

^aCollege of Forestry and Landscape Architecture, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture, South China Agricultural University, Guangzhou 510642, Guangdong, China
^bCollege of Materials and Energy, South China Agricultural University, Guangzhou 510642, Guangdong, China
^cState Center for International Cooperation on Designer Low-Carbon & Environmental Materials (CDLCEM), School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^dState Key Laboratory of Electronic Thin Film and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^eSchool of Energy and Environment, City University of Hong Kong, Hong Kong SAR

Received:2020-03-02 Accepted:2020-04-21 Online:2021-01-18 Published:2021-01-18
Contact: Yun Hau Ng,Xin Li
About author:^#E-mail: yunhau.ng@cityu.edu.hk
^*Tel: +86-20-85282633; Fax: +86-20-85285596; E-mail: Xinliscau@yahoo.com;
Supported by:
National Natural Science Foundation of China(21975084);National Natural Science Foundation of China(51672089);Specical Funding on Applied Science and Technology in Guangdong(2017B020238005);State Key Laboratory of Advanced Technology for Material Synthesis and Processing (Wuhan University of Technology)(2015-KF-7);Hong Kong Research Grant Council (RGC) General Research Fund(GRF13054)

摘要/Abstract

摘要：

开发低成本的半导体光催化剂以实现可见光下高效、持久的光催化分解水产氢化是一个非常具有挑战性的课题. 近年来, 具有孪晶结构的Zn_xCd_1-_xS (ZCS)固溶体引起了人们的研究兴趣, 这主要是由于孪晶相之间形成了同质结, 同质结可以通过提高体相光生电子-空穴对的分离效率, 从而提高原始硫化物光催化剂的光催化分解水产氢活性. 但由于孪晶ZCS固溶体表面超快载流子复合以及活性位点不足, 进一步提高其光催化析氢活性还需解决这些不足. 负载助催化剂被认为是加速产氢动力学和促进表面光生电子空穴分离最有效策略之一. 因此, 我们将低成本的类金属Ni₃C助催化剂与孪晶ZCS固溶体通过简单的研磨方法结合来实现高效的可见光催化分解水产氢. 合成的Zn_0.5Cd_0.5S-1% Ni₃C (ZCS-1)异质结/同质结最高的可见光光催化分解水产氢速率可达783 μmol h^-1, 是纯ZCS的2.88倍. 在420 nm时, ZCS和ZCS-1的表观量子效率分别为6.13%和19.25%. 这是由于孪晶ZCS固溶体中闪锌矿段和纤锌矿段的同质结连接可以显著提高光生电子空穴对的体相转移和分离. 同时, ZCS与金属Ni₃C助催化剂间的异质结可以有效地增加孪晶ZCS固溶体的光捕获及表面载流子分离, 增强产氢活性位, 从而提高催化活性.
本文以乙酸镉、乙酸锌和氢氧化钠为原料合成了CdZn(OH), 后者与硫代乙酰胺水热合成了孪晶CZS, 并用超声研磨方法合成CZS-Ni₃C. 在可见光下进行了产氢测试, 实验结果证实了优化的ZCS-1在Na₂S·9H₂O和Na₂SO₃的水溶液中光催化析氢活性最高. 经过4次连续的循环反应, ZCS-1二元复合体系展现出良好的稳定性. 为深入探讨高效产氢机制, 对纳米级ZCS复合材料的光催化物化性能及载流子分离机制进行了表征. 通过X射线衍射确定了ZCS和ZCS-1的晶体结构. 用高分辨电子显微镜和X射线光电子能谱证实合成了ZCS和Ni₃C助催化剂的成功复合. 用紫外-可见漫反射光谱法对制备的ZCS和ZCS-1复合样品的光吸收特性进行了表征. 结果表明, 在ZCS上负载Ni₃C以后, 样品的可见光吸收能力显著提升. 利用稳态及瞬态荧光光谱研究了ZCS-1光催化剂的电荷载流子复合和转移行为. 进一步对纯ZCS和ZCS-1复合光催化剂的瞬态光电流响应(I-t曲线)进行了研究, 确定了光生载体的分离效率. 阻抗是深入研究电荷载流子迁移和界面转移的最有力技术, 利用阻抗技术证实ZCS-1界面高效的载流子分离性能. 极化曲线结果表明, 加入Ni₃C可以降低ZCS的产氢过电势, 因此加速表面产氢动力学.
由此可见, 本文所构建的ZCS同质结与Ni₃C助催化剂的协同作用可以明显促进体相及表面光生电子空穴对的分离, 从而显著增强光催化分解水产氢活性. 该文所采用基于ZCS纳米孪晶与异质助催化剂耦合策略可以作为一种通用策略扩展到各种传统半导体的改性, 从而极大地推进高效光催化产氢材料的持续进步.

关键词: 可见光光催化产氢, Zn_0.5Cd_0.5S固溶体, 孪晶, 同质结异质结, 廉价Ni₃C助催化剂

Abstract:

The development of low-cost semiconductor photocatalysts for highly efficient and durable photocatalytic H₂ evolution under visible light is very challenging. In this study, we combine low-cost metallic Ni₃C cocatalysts with twin nanocrystal Zn_0.5Cd_0.5S (ZCS) solid solution homojunctions for an efficient visible-light-driven H₂ production by a simple approach. As-synthesized Zn_0.5Cd_0.5S-1% Ni₃C (ZCS-1) heterojunction/homojunction nanohybrid exhibited the highest photocatalytic H₂-evolution rate of 783 μmol h^-1 under visible light, which is 2.88 times higher than that of pristine twin nanocrystal ZCS solid solution. The apparent quantum efficiencies of ZCS and ZCS-1 are measured to be 6.13% and 19.25% at 420 nm, respectively. Specifically, the homojunctions between the zinc blende and wurtzite segments in twin nanocrystal ZCS solid solution can significantly improve the light absorption and separation of photogenerated electron-hole pairs. Furthermore, the heterojunction between ZCS and metallic Ni₃C NP cocatalysts can efficiently trap excited electrons from ZCS solid solution and enhance the H₂-evolution kinetics at the surface for improving catalytic activity. This study demonstrates a unique one-step strategy for constructing heterojunction/homojunction hybrid nanostructures for a more efficient photocatalytic H₂ evolution compared to other noble metal photocatalytic systems.

Key words: Photocatalytic H₂ evolution, Zn_0.5Cd_0.5S solid solution, Twin nanocrystal, Heterojunction/homojunction, Earth-abundant Ni₃C cocatalysts

沈荣晨, 丁英娜, 李世邦, 张鹏, 向全军, 吴永豪, 李鑫. 构建低成本的Ni₃C/孪晶Zn_0.5Cd_0.5S异质结/同质结纳米杂化体系来实现高效的光催化分解水产氢[J]. 催化学报, 2021, 42(1): 25-36.

Rongchen Shen, Yingna Ding, Shibang Li, Peng Zhang, Quanjun Xiang, Yun Hau Ng, Xin Li. Constructing low-cost Ni₃C/twin-crystal Zn_0.5Cd_0.5S heterojunction/homojunction nanohybrids for efficient photocatalytic H₂ evolution[J]. Chinese Journal of Catalysis, 2021, 42(1): 25-36.

×
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(20)63600-2

https://www.cjcatal.com/CN/Y2021/V42/I1/25

图/表 14

Fig. 1. (A, B, D, E) TEM images of twin nanocrystal ZCS solid solution, (C) HRTEM image of twin nanocrystal ZCS solid solution, (F) FFT pattern indicating that the twins in each grain are parallel to each other in (111) planes.

Fig. 2. (A) TEM image of Ni3C NPs; TEM (B) and HRTEM (C) images of ZCS-1; (E-I) Corresponding elemental mapping of ZCS-1.

Table 1 Experimental data of EDS of ZCS-1.

Sample	Atomic fraction (at%)						Weight fraction (wt%)
ZCS	Zn	Cd	S	Ni	C		Zn	Cd	S	Ni	C
ZCS-1	15.33	15.58	30.54	0.56	37.99		23.68	41.47	23.23	0.79	10.83

Fig. 3. XRD patterns of the twin nanocrystal Zn1-xCdxS solid solution with different Zn/Cd molar ratios (A), ZCS-X composites and Ni3C (B).

Fig. 4. XPS survey profile (A) and high-resolution XPS profile of Zn 2p (B), Cd 3d (C), S 2p (D), Ni 2p (E), and C 1s (F) of the ZCS-1 sample.

Fig. 5. (A) N2 adsorption-desorption isotherms and the corresponding pore size distribution curves (inset) of ZCS and ZCS-1. (B) BET surface areas and pore volumes of ZCS and ZCS-1.

Fig. 6. (A) UV-vis absorption spectra of as-prepared samples and optical images of samples (inset); (B) Tauc plots of the UV-vis spectra.

Fig. 7. Time courses (A) and average rates (B) of H2 evolution over different composite photocatalysts. (C) Comparison of H2 evolution activities of Ni3C, twin nanocrystal Zn1-xCdxS solid solutions with different Zn/Cd ratios, ZCS-1 composite, and ZCS-1%Pt. (D) Wavelength dependence of the apparent quantum efficiencies for the ZCS-1 sample. Reaction conditions: 50 mg of catalyst; 80 mL of 0.25 M Na2S-Na2SO3 aqueous solution; xenon lamp (300 W) light source with a UV cutoff filter (λ ≥ 420 nm).

Fig. 8. Repeated time courses of photocatalytic H2 evolution on ZCS-1 (A) and ZCS (B) samples. Reaction conditions: 50 mg of catalyst; 80 mL of 0.25 M Na2S-Na2SO3 aqueous solution; xenon lamp (350 W) light source with a UV cutoff filter (λ ≥ 420 nm).

Fig. 9. PL spectra (A) transient photocurrent responses (I-t curves) (B), electrochemical impedance spectroscopy Nyquist plots (C), and Mott-Schottky (MS) plots (D) of ZCS and ZCS-1 photocatalysts.

Fig. 10. Time-resolved transient PL decay of twin nanocrystal ZCS solid solution (A) and ZCS-1 (B).

Fig. 11. Polarization curves of the photocatalysts were measured at a scan rate of 5 mV s-1 in 0.5 M H2SO4 solution (A) and 0.25 M Na2S-Na2SO3 aqueous solution (B).

Fig. 12. Valence-band XPS profile of twin nanocrystal ZCS solid solution (ZCS) (A), ZCS-1 (B), corresponding bandgap structures (C) of two photocatalysts.

Scheme 1. Proposed photocatalytic H2 evolution and charge transfer mechanisms in the Ni3C/Zn0.5Cd0.5S composite photocatalyst under visible light irradiation.

参考文献

[1]	A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[2]	J. Wen, J. Xie, X. Chen, X. Li, Appl. Surf. Sci., 2017, 391, 72-123.
[3]	X. Li, J. Yu, J. Low, Y. Fang, J. Xiao, X. Chen, J. Mater. Chem. A, 2015, 3, 2485-2534.
[4]	H. M. Zhao, Y. F. He, M. Y. Liu, R. Wang, Y. H. Li, W. S. You, Chin. J. Catal., 2018, 39, 495-501.
[5]	L. Cheng, Q. J. Xiang, Y. L. Liao, H. W. Zhang, Energy Environ. Sci., 2018, 11, 1362-1391.
[6]	K. Zhang, L. J. Guo, Catal. Sci. Technol., 2013, 3, 1672-1690.
[7]	H. G. Yu, W. Zhong, X. Huang, P. Wang, J. G. Yu, ACS Sustain. Chem. Eng., 2018, 6, 5513-5523.
[8]	K. Chang, M. Li, T. Wang, S. Ouyang, P. Li, L. Liu, J. Ye, Adv. Energy Mater., 2015, 5, 1402279.
[9]	S. Ma, J. Xie, J. Wen, K. He, X. Li, W. Liu, X. Zhang, Appl. Surf. Sci., 2017, 391, 580-591.
[10]	Q. Xiang, B. Cheng, J. Yu, Appl. Catal. B, 2013, 138-139, 299-303.
[11]	Z. W. Zhang, Q. H. Li, X. Q. Qiao, D. F. Hou, D. S. Li, Chin. J. Catal., 2019, 40, 371-379.
[12]	Y. Tang, P. Traveerungroj, H. L. Tan, P. Wang, R. Amal, Y. H. Ng, J. Mater. Chem. A, 2015, 3, 19582-19587.
[13]	H. Wu, Z. Zheng, Y. Tang, N. M. Huang, R. Amal, H. N. Lim, Y. H. Ng, Sustain. Mater. Technol., 2018, 18, e00075.
[14]	M. Liu, L. Wang, G. Lu, X. Yao, L. Guo, Energy Environ. Sci., 2011, 4, 1372.
[15]	J. Song, H. Zhao, R. Sun, X. Li, D. Sun, Energy Environ. Sci., 2017, 10, 225-235.
[16]	T. P. Hu, P. F. Li, J. F. Zhang, C. H. Liang, K. Dai, Appl. Surf. Sci., 2018, 442, 20-29.
[17]	W. Zhong, X. Huang, Y. Xu, H. Yu, Nanoscale, 2018, 10, 19418-19426.
[18]	M. Liu, D. Jing, Z. Zhou, L. Guo, Nat. Commun., 2013, 4, 2278.
[19]	M. Liu, Y. Chen, J. Su, J. Shi, X. Wang, L. Guo, Nature Energy, 2016, 1, 16151.
[20]	H. Du, H. L. Guo, Y. N. Liu, X. Xie, K. Liang, X. Zhou, X. Wang, A. W. Xu, ACS Appl. Mater. Interfaces, 2016, 8, 4023-4030.
[21]	Y. Hao, S.-Z. Kang, X. Liu, X. Li, L. Qin, J. Mu, ACS Sustain. Chem. Eng., 2017, 5, 1165-1172.
[22]	P. Wang, Y. Sheng, F. Wang, H. Yu, Appl. Catal. B, 2018, 220, 561-569.
[23]	D. C. Jiang, L. Zhu, R. M. Irfan, L. Zhang, P. W. Du, Chin. J. Catal., 2017, 38, 2102-2109.
[24]	J. Z. Su, T. Zhang, L. Wang, J. W. Shi, Y. B. Chen, Chin. J. Catal., 2017, 38, 489-497.
[25]	L. J. Zhang, X. Q. Hao, Y. P. Wang, Z. L. Jin, Q. X. Ma, Chem. Eng. J., 2019, 376, 123545.
[26]	S. Ma, X. Xu, J. Xie, X. Li, Chin. J. Catal., 2017, 38, 1970-1980.
[27]	R. K. Chava, J. Y. Do, M. Kang, ACS Sustain. Chem. Eng., 2018, 6, 6445-6457.
[28]	D. Gao, W. Liu, Y. Xu, P. Wang, J. Fan, H. Yu, Appl. Catal. B, 2020, 260, 118190.
[29]	Z. W. Zhang, Q. H. Li, X. Q. Qiao, D. F. Hou, D. S. Li, Chin. J. Catal., 2019, 40, 371-379.
[30]	B. Chai, C. Liu, C. Wang, J. Yan, Z. Ren, Chin. J. Catal., 2017, 38, 2067-2075.
[31]	R. C. Shen, J. Xie, Q. J. Xiang, X. B. Chen, J. Z. Jiang, X. Li, Chin. J. Catal., 2019, 40, 240-288.
[32]	J. Zhang, L. F. Qi, J. R. Ran, J. G. Yu, S. Z. Qiao, Adv. Energy Mater., 2014, 4, 130192.
[33]	B. Q. Wang, Y. Ding, Z. R. Deng, Z. H. Li, Chin. J. Catal., 2019, 40, 335-342.
[34]	P. Wang, S. Q. Xu, F. Chen, H. G. Yu, Chin. J. Catal., 2019, 40, 343-351.
[35]	J. Yuan, J. Wen, Q. Gao, S. Chen, J. Li, X. Li, Y. Fang, Dalton Trans., 2015, 44, 1680-1689.
[36]	D. S. Dai, H. Xu, L. Ge, C. C. Han, Y. Q. Gao, S. S. Li, Y. Lu, Appl. Catal. B, 2017, 217, 429-436.
[37]	B. J. Ma, R. S. Zhang, K. Y. Lin, H. X. Liu, X. Y. Wang, W. Y. Liu, H. J. Zhan, Chin. J. Catal., 2018, 39, 527-533.
[38]	Y. B. Li, Z. L. Jin, T. S. Zhao, Chem. Eng. J., 2019, 382, 123051.
[39]	Y.-X. Pan, J.-B. Peng, S. Xin, Y. You, Y.-L. Men, F. Zhang, M.-Y. Duan, Y. Cui, Z.-Q. Sun, J. Song, ACS Sustain. Chem. Eng., 2017, 5, 5449-5456.
[40]	D. S. Dai, L. Wang, N. Xiao, S. S. Li, H. Xu, S. Liu, B. R. Xu, D. Lv, Y. Q. Gao, W. Y. Song, L. Ge, J. Liu, Appl. Catal. B, 2018, 233, 194-201.
[41]	S. Q. Peng, Y. Yang, J. N. Tan, C. Gan, Y. X. Li, Appl. Surf. Sci., 2018, 447, 822-828.
[42]	W. T. Bi, L. Zhang, Z. T. Sun, X. G. Li, T. Jin, X. J. Wu, Q. Zhang, Y. Luo, C. Z. Wu, Y. Xie, ACS Catal., 2016, 6, 4253-4257.
[43]	K. He, J. Xie, Z. Yang, R. Shen, Y. Fang, S. Ma, X. Chen, X. Li, Catal. Sci. Technol., 2017, 7, 1193-1202.
[44]	S. Ma, Y. Deng, J. Xie, K. He, W. Liu, X. Chen, X. Li, Appl. Catal. B, 2018, 227, 218-228.
[45]	J. Ran, G. Gao, F. T. Li, T. Y. Ma, A. Du, S. Z. Qiao, Nat. Commun., 2017, 8, 13907.
[46]	Z. Luo, X. Zhao, H. Zhang, Y. Jiang, Appl. Catal. A, 2019, 582, 117115.
[47]	J. Wen, J. Xie, Z. Yang, R. Shen, H. Li, X. Luo, X. Chen, X. Li, ACS Sustain. Chem. Eng., 2017, 5, 2224-2236.
[48]	R. Shen, J. Xie, X. Lu, X. Chen, X. Li, ACS Sustain. Chem. Eng., 2018, 6, 4026-4036.
[49]	R. Shen, J. Xie, H. Zhang, A. Zhang, X. Chen, X. Li, ACS Sustain. Chem. Eng., 2018, 6, 816-826.
[50]	K. He, J. Xie, M. Li, X. Li, Appl. Surf. Sci., 2018, 430, 208-217.
[51]	K. He, J. Xie, Z. Q. Liu, N. Li, X. B. Chen, J. Hu, X. Li, J. Mater. Chem. A, 2018, 6, 13110-13122.
[52]	R. Shen, W. Liu, D. Ren, J. Xie, X. Li, Appl. Surf. Sci., 2019, 466, 393-400.
[53]	X. Fan, Z. Peng, R. Ye, H. Zhou, X. Guo, ACS Nano, 2015, 9, 7407-7418.
[54]	R. T. Chiang, R. K. Chiang, F. S. Shieu, RSC Adv., 2014, 4, 19488.
[55]	Q. Li, H. Meng, P. Zhou, Y. Q. Zheng, J. Wang, J. G. Yu, J. R. Gong, ACS Catal., 2013, 3, 882-889.
[56]	J. Yuan, J. Wen, Y. Zhong, X. Li, Y. Fang, S. Zhang, W. Liu, J. Mater. Chem. A, 2015, 3, 18244-18255.
[57]	S. Iqbal, Z. Pan, K. Zhou, Nanoscale, 2017, 9, 6638-6642.
[58]	J. Wen, X. Li, H. Li, S. Ma, K. He, Y. Xu, Y. Fang, W. Liu, Q. Gao, Appl. Surf. Sci., 2015, 358, 204-212.
[59]	Z. Zhang, J. Huang, M. Zhang, Q. Yuan, B. Dong, Appl. Catal. B, 2015, 163, 298-305.
[60]	Z. Bian, T. Tachikawa, W. Kim, W. Choi, T. Majima, J. Phys. Chem. C, 2012, 116, 25444-25453.
[61]	Y. Y. Hsu, N. T. Suen, C. C. Chang, S. F. Hung, C. L. Chen, T. S. Chan, C. L. Dong, C. C. Chan, S. Y. Chen, H. M. Chen, ACS Appl. Mater. Interfaces, 2015, 7, 22558-22569.

构建低成本的Ni₃C/孪晶Zn_0.5Cd_0.5S异质结/同质结纳米杂化体系来实现高效的光催化分解水产氢

Constructing low-cost Ni₃C/twin-crystal Zn_0.5Cd_0.5S heterojunction/homojunction nanohybrids for efficient photocatalytic H₂ evolution

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 14

参考文献

相关文章 1

编辑推荐

Metrics