表面缺陷与钯的沉积对硫化镉纳米晶粒的光催化制氢性能的影响

doi:10.3866/PKU.WHXB201803061

摘要/Abstract

摘要：

近年来，光解水制氢的发展引起了人们的高度关注。CdS是一种具有可见光响应的很有潜力光催化剂，但由于光生电子/空穴对的快速复合和表面上的析氢反应速率低，所以它仅表现出有限的光解水制氢活性。对CdS表面结构和性能的影响的研究仍然非常有限。在本工作中，我们制备了三种具有不同形貌的CdS纳米晶体(长棒状，短棒状和三角片状)用于光解水制氢。随着纵横比的增加，非极性表面暴露面积增大，表面缺陷程度也随之增加，而表面缺陷可以捕获光生电子/空穴，从而降低其复合机会。我们发现氢的生产率可能与表面缺陷的程度有关。另外，这些缺陷可以用来固定Pd粒子形成异质结结构，有利于光生电荷的分离。在1% (w,质量分数) Pd的协助下，所有CdS催化剂的氢气产率都大大提高。值得注意的是，sr-CdS/Pd的制氢产率达到了7884 μmol·h^-1·g^-1，与文献报道的最高值相当。希望本文能够为了解晶体结构和性能对光催化的影响提供认识。

关键词: CdS纳米晶体, 光催化制氢, 表面缺陷, 异质结, Pd促进作用

Abstract:

The development of the photocatalytic production of hydrogen from water splitting has attracted immense attention in recent years. CdS is a potential photocatalyst with a visible light response, though it still suffers from a limited activity for hydrogen production due to the fast recombination of photo-induced electron/hole pairs and the low reaction rate of hydrogen evolution on the surface. Studies on the effect of CdS surface structure and properties on hydrogen production are still very limited. In this work, we prepared three CdS nanocrystals with different morphologies: long rod, short rod, and triangular plate. The prepared samples were well characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area analysis, X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). From the results of TEM, XRD and XPS, we find that the three CdS nanocrystals with different morphologies were successfully synthesized. From the PL spectra, we conclude that the area of exposed nonpolar surface and degree of surface defects increase with an increase in aspect ratio. We also performed the photocatalytic hydrogen production reaction using the three CdS crystals. Long rod-like CdS (lr-CdS) exhibits the highest photocatalytic activity, with a hydrogen production rate of 482 μmol·h^-1·g^-1, which is 2.6 times that of short rod-like CdS (sr-CdS) (183 μmol·h^-1·g^-1) and 8.8 times that of triangular plate-like CdS (tp-CdS, 55 μmol h^-1·g^-1). It is found that lr-CdS shows a higher hydrogen production rate than sr-CdS and tp-CdS. We find that the hydrogen production rate is related to the degree of surface defects. Surface defects can trap the photo-induced electrons/holes, thus decreasing their probability of recombination. In addition, these defects can be used to anchor Pd particles to form a heterojunction structure that facilitates the separation of photo-induced charges. Therefore, we also compared three CdS/Pd nanocrystals synthesized with the three abovementioned morphologies with respect to hydrogen production. With 1% (w, mass fraction) Pd, the hydrogen production rate was greatly enhanced compared to all the CdS catalysts. Compared to the unpromoted CdS, the reaction rate is enhanced 43.1, 10.7 and 6.0 times over those of sr-CdS, lr-CdS and tp-CdS, respectively. Notably, the hydrogen production rate with short rod-like CdS/Pd reaches 7884 μmol·h^-1·g^-1, which can be favorably compared with the ever-increasing values reported in the literature. Hopefully, this work provides knowledge on the effect of crystal surface structure and properties on photocatalysis.

Key words: CdS nanocrystal, Photocatalytic hydrogen production, Surface defects, Heterojunction structure, Pd promotion

MSC2000:

O643

刘志明, 刘国亮, 洪昕林. 表面缺陷与钯的沉积对硫化镉纳米晶粒的光催化制氢性能的影响[J]. 物理化学学报, 2019, 35(2): 215-222.

Zhiming LIU, Guoliang LIU, Xinlin HONG. Influence of Surface Defects and Palladium Deposition on the Activity of CdS Nanocrystals for Photocatalytic Hydrogen Production[J]. Acta Phys. -Chim. Sin., 2019, 35(2): 215-222.

参考文献

1	Chen J. ; Shen S. H. ; Guo P. H. ; Wang M. ; Wu P. ; Wang X. X. ; Guo L. J. Appl. Catal. B-Environ. 2014, 152-153, 335.
2	Acar C. ; Dincer L. ; Naterer G. F. Int. J. Energy Res. 2016, 40, 1449.
3	Xu Y. ; Xu R. Appl. Surf. Sci. 2015, 351, 779.
4	Wang F. M. ; Shifa T. A. ; Zhan X. Y. ; Huang Y. ; Liu K. L. ; Cheng Z. Z. ; Jiang C. ; He J. Nanoscale 2015, 7, 19764.
5	Osterloh F. E. Chem. Soc. Rev. 2013, 42, 2294.
6	Ni M. ; Leung M. K. H. ; Leung D. Y. C. ; Sumathy K. Renew. Sust. Energ. Rev. 2007, 11, 401.
7	Hisatomi T. ; Kubota J. ; Domen K. Chem. Soc. Rev. 2014, 43, 7520.
8	Chen X. B. ; Shen S. H. ; Guo L. J. ; Mao S. S. Chem. Rev. 2010, 110, 6503.
9	Tong H. ; Ouyang S. X. ; Bi Y. P. ; Umezawa N. ; Oshikiri M. ; Ye J. H. Adv. Mater. 2012, 24, 229.
10	Liao C. H. ; Huang C. W. ; Wu J. C. S. Catalysts 2012, 2, 490.
11	Kudo A. ; Miseki Y. Chem. Soc. Rev. 2009, 38, 253.
12	Banerjee S. ; Pillai S. C. ; Falaras P. ; O'Shea K. E. ; Byrne J. A. ; Dionysiou D. D. J. Phys. Chem. Lett. 2014, 5, 2543.
13	Asahi R. ; Morikawa T. ; Irie H. ; Ohwaki T. Chem. Rev. 2014, 114, 9824.
14	Irie H. ; Miura S. ; Kamiya K. ; Hashimoto K. Chem. Phys. Lett. 2008, 457, 202.
15	Ouyang S. X. ; Ye J. H. J. Am. Chem. Soc. 2011, 133, 7757.
16	Shenawi-Khalil S. ; Uvarov V. ; Kritsman Y. ; Menes E. ; Popov I. ; Sasson Y. Catal. Commun. 2011, 12, 1136.
17	Hu C. C. ; Lee Y. L. ; Teng H. J. Phys. Chem. C 2011, 115, 2805.
18	Yun H. J. ; Lee H. ; Kim N. D. ; Lee D. M. ; Yu S. ; Yi J. ACS Nano 2011, 5, 4084.
19	Li C. X. ; Han L. J. ; Liu R. J. ; Li H. H. ; Zhang S. J. ; Zhang G. J. J. Mater. Chem. 2012, 22, 23815.
20	Bao N. Z. ; Shen L. M. ; Takata T. ; Domen K. Chem. Mater. 2008, 20, 110.
21	Silva L. A. ; Ryu S. Y. ; Choi J. ; Choi Y. ; Hoffmann M. R. J. Phys. Chem. C 2008, 112, 12069.
22	Yu J. G. ; Yu Y. F. ; Cheng B. RSC Adv. 2012, 2, 11829.
23	Jin J. ; Yu J. G. ; Liu G. ; Wong P. K. J. Mater. Chem. A 2013, 1, 10927.
24	Zhang K. ; Guo L. J. Catal. Sci. Technol. 2013, 3, 1672.
25	Yang J. H. ; Wang D. ; Han H. X. ; Li C. Acc. Chem. Res. 2013, 46, 1900.
26	Shi H. Y. ; Yan R. S. ; Bertolazzi S. ; Brivio J. ; Gao B. ; Kis A. ; Jena D. ; Xing H. G. ; Huang L. B. ACS Nano 2013, 7, 1072.
27	Tongay S. ; Suh J. ; Ataca C. ; Fan W. ; Luce1 A. ; Kang J. S. ; Liu J. ; Ko C. ; Raghunathanan R. ; Zhou J. ; et al Sci. Rep. 2013, 3, 2657.
28	Chen W. ; Chen K. B. ; Peng Q. ; Li Y. D. Small 2009, 5, 681.
29	Wang X. L. ; Feng Z. C. ; Fan D. Y. ; Fan F. T. ; Li C. Cryst. Growth Des. 2010, 10, 5312.
30	Yan H. J. ; Yang J. H. ; Ma G. J. ; Wu G. P. ; Zong X. ; Lei Z. B. ; Shi J. Y. ; Li C. J. Catal. 2009, 266, 165.
31	Yang J. H. ; Yan H. J. ; Wang X. L. ; Wen F. Y. ; Wang Z. J. ; Fan D. Y. ; Shi J. Y. ; Li C. J. Catal. 2012, 290, 151.
32	Tauc J. ; Grigorovici R. ; Vancu A. Phys. Stat. Sol. 1966, 15, 627.
33	Zhang H. ; Cai J. M. ; Wang Y. T. ; Wu M. Q. ; Meng M. ; Tian Y. ; Li X. G. ; Zhang J. ; Zheng L. R. ; Jiang Z. ; et al Appl. Catal. B- Environ. 2018, 220, 126.
34	Cai J. M. ; Wu M. Q. ; Wang Y. T. ; Zhang H. ; Meng M. ; Tian Y. ; Li X. G. ; Zhang J. ; Zheng L. R. ; Gong J. L. Chem 2017, 2, 877.
35	Wang Y. T. ; Cai J. M. ; Wu M. Q. ; Zhang H. ; Meng M. ; Tian Y. ; Ding T. ; Gong J. L. ; Jiang Z. ; Li X. G. ACS Appl. Mater. Interfaces 2016, 8, 23006.
36	Cai J. M. ; Wang Y. T. ; Zhu Y. M. ; Wu M. Q. ; Zhang H. ; Li X. G. ; Jiang Z. ; Meng M. ACS Appl. Mater. Interfaces 2015, 7, 24987.
37	Peng T. Y. ; Li K. ; Zeng P. ; Zhang Q. G. ; Zhang X. G. J. Phys. Chem. C 2012, 116, 22720.
38	Cheng F. Y. ; Yin H. ; Xiang Q. J. Appl. Surf. Sci. 2017, 391, 432.
39	Jia T. T. ; Kolpin A. ; Ma C. S. ; Chan R. C. T. ; Kwok W. M. ; Tsang S. C. E. Chem. Commun. 2014, 50, 1185.
40	Xiang Q. J. ; Cheng F. Y. ; Lang D. ChemSusChem 2016, 9, 996.
41	Zeng P. ; Zhang Q. G. ; Peng T. Y. ; Zhang X. H. Phys. Chem. Chem. Phys. 2011, 13, 21496.
42	Du X. H. ; Li Y. ; Yin H. ; Xiang Q. J. Acta Phys. -Chim. Sin. 2018, 34, 414.
42	杜新华; 李阳; 殷辉; 向全军. 物理化学学报, 2018, 34, 414.
43	Zhang C. ; Wu Z. J. ; Liu J. J. ; Piao L. Y. Acta Phys. -Chim. Sin. 2017, 33, 1492.
43	张驰; 吴志娇; 刘建军; 朴玲钰. 物理化学学报, 2017, 33, 1492.

[1]	韩高伟, 徐飞燕, 程蓓, 李佑稷, 余家国, 张留洋. 反蛋白石结构ZnO@PDA用于增强光催化产H₂O₂性能[J]. 物理化学学报, 2022, 38(7): 2112037 - .
[2]	周亮, 李云锋, 张永康, 秋列维, 邢艳. 具有高效界面电荷转移的0D/2D Bi₄V₂O₁₁/g-C₃N₄梯形异质结的设计合成及抗生素降解性能研究[J]. 物理化学学报, 2022, 38(7): 2112027 - .
[3]	王文亮, 张灏纯, 陈义钢, 史海峰. 具有光催化与光芬顿反应协同作用的2D/2D α-Fe₂O₃/g-C₃N₄ S型异质结用于高效降解四环素[J]. 物理化学学报, 2022, 38(7): 2201008 - .
[4]	刘珊池, 王凯, 杨梦雪, 靳治良. Mn_0.2Cd_0.8S@CoAl LDH S-型异质结构建及其光催化析氢性能研究[J]. 物理化学学报, 2022, 38(7): 2109023 - .
[5]	黄悦, 梅飞飞, 张金锋, 代凯, Graham Dawson. 一维/二维W₁₈O₄₉/多孔g-C₃N₄梯形异质结构建及其光催化析氢性能研究[J]. 物理化学学报, 2022, 38(7): 2108028 - .
[6]	朱弼辰, 洪小洋, 唐丽永, 刘芹芹, 唐华. 二维/一维BiOBr_0.5Cl_0.5/WO₃ S型异质结助力光催化CO₂还原[J]. 物理化学学报, 2022, 38(7): 2111008 - .
[7]	邹菁云, 高冰, 张小品, 唐磊, 冯思敏, 金赫华, 刘碧录, 成会明. 一维碳纳米管/二维二硫化钼混合维度异质结的原位制备及其电荷转移性能[J]. 物理化学学报, 2022, 38(5): 2008037 - .
[8]	李红英, 龚海明, 靳治良. In₂O₃修饰三维纳米花MoS_x构建S型异质结用于高效光催化产氢[J]. 物理化学学报, 2022, 38(12): 2201037 - .
[9]	李瀚, 李芳, 余家国, 曹少文. 二维/二维FeNi-LDH/g-C₃N₄复合光催化剂用于促进CO₂光还原反应[J]. 物理化学学报, 2021, 37(8): 2010073 - .
[10]	李云锋, 张敏, 周亮, 杨思佳, 武占省, 马玉花. g-C₃N₄表面改性及其光催化制H₂与CO₂还原研究进展[J]. 物理化学学报, 2021, 37(6): 2009030 - .
[11]	梅子慧, 王国宏, 严素定, 王娟. 微波辅助快速制备2D/1D ZnIn₂S₄/TiO₂ S型异质结及其光催化制氢性能[J]. 物理化学学报, 2021, 37(6): 2009097 - .
[12]	费新刚, 谭海燕, 程蓓, 朱必成, 张留洋. 理论计算研究二维/二维BP/g-C₃N₄异质结的光催化CO₂还原性能[J]. 物理化学学报, 2021, 37(6): 2010027 - .
[13]	李喜宝, 刘积有, 黄军同, 何朝政, 冯志军, 陈智, 万里鹰, 邓芳. 全有机S型异质结PDI-Ala/S-C₃N₄光催化剂增强光催化性能[J]. 物理化学学报, 2021, 37(6): 2010030 - .
[14]	刘东, 陈圣韬, 李仁杰, 彭天右. 用于光催化能量转换的Z-型异质结的研究进展[J]. 物理化学学报, 2021, 37(6): 2010017 - .
[15]	赫荣安, 陈容, 罗金花, 张世英, 许第发. 石墨烯量子点修饰的BiOI/PAN柔性纤维的制备及其增强的光催化活性[J]. 物理化学学报, 2021, 37(6): 2011022 - .