碳包覆Pd/TiO2光催化产氢协同胺类选择性氧化合成亚胺

doi:10.3866/PKU.WHXB202211029

摘要/Abstract

摘要：

负载型金属纳米催化剂由于其优异的光催化性能，被广泛应用于光催化产氢协同胺类氧化偶联合成高附加值亚胺体系。但在反应过程中，金属表面对H原子和亚胺表现出较强的吸附能力，导致了亚胺易于发生自氢化反应而生成仲胺，显著降低了亚胺的选择性。在本文中，我们证实了在Pd/TiO₂表面构建超薄碳层(Pd/TiO₂@C)是一种解决上述问题的有效策略。在Pd/TiO₂表面构筑的超薄碳层可以有效调控H原子和亚胺在其表面的吸附行为，避免了光催化氧化偶联过程中亚胺的自氢化。因此，Pd/TiO₂@C光催化剂在光催化产氢协同胺类选择性氧化合成亚胺体系中展现出优异的亚胺选择性。本研究提供了一种便捷有效的策略推动负载型金属纳米催化剂在光催化产氢协同合成高附加值产物体系中的应用。

关键词: 光催化, 析氢反应, 胺氧化偶联, 负载型金属催化剂, 表面修饰

Abstract:

Supported metal nanocatalysts are promising candidates for heterogenous photocatalysis because the metal nanoparticles (e.g., Au, Pt, or Pd) loaded on the semiconductor surface not only act as a reductive cocatalyst, which accelerates the kinetics of reactions such as H⁺ reduction, but also trap the photoelectrons, which allows charge separation. Owing to these unique benefits, supported metal photocatalysts have been extensively studied for green H₂ production at the reductive side integrated with organic selective oxidation at the oxidative side in a closed photocatalytic redox cycle. Imines and their derivatives are important chemicals in the industrial production of functional polymers, agrochemicals, and pharmaceuticals. Recently, imines have been successfully produced via the photocatalytic dehydrogenative coupling of amines over supported metal nanocatalysts. However, owing to the strong adsorption of H atoms and imines on the metal surface, the produced imines are converted to secondary amines via a self-hydrogenation process, thus greatly decreasing the selectivity toward the desired imines. Herein, we demonstrate that the construction of an ultrathin carbon layer on a Pd/TiO₂ photocatalyst (Pd/TiO₂@C) via the thermal annealing of self-assembled polydopamine layers is a simple yet effective strategy to address this issue. Temperature-programmed reduction of hydro-oxygen titration and cyclic voltammetry curves for Pd/TiO₂vs. Pd/TiO₂@C indicate that the conformable coating of the carbon layer on the catalyst surface facilitates kinetic control of H atom adsorption on the supported Pd nanoparticles. Furthermore, in situ Fourier-transform infrared spectroscopy demonstrates that the conformably coated ultrathin carbon layer also decreases the adsorption of substrate molecules such as N-benzylidenebenzylamine on the catalyst surface, which weakens their interaction with the supported Pd nanoparticles. Thus, the construction of an ultrathin conformable carbon coating on Pd/TiO₂ is a facile strategy to kinetically control the adsorption behavior of H atoms and imines on the Pd surface during photocatalytic redox reactions, which can suppress the excessive hydrogenation of imines toward selectivity improvement. In addition, owing to the strong electronic interaction between the Pd nanoparticles and the carbon layer, the encapsulated Pd nanoparticles retain their unique catalytic properties toward the H₂ evolution reaction. As a result, Pd/TiO₂@C with an optimized carbon layer thickness facilitates improved photocatalytic synthesis of imines, with conversion and selectivity as high as 95% and 99%, respectively. This study provides an effective strategy to develop high-performance supported metal nanocatalysts for integrated photocatalytic systems to produce H₂ and valuable organic chemicals.

Key words: Photocatalysis, Hydrogen evolution reaction, Amine oxidative coupling, Supported metal nanocatalysts, Surface modification

点击下载补充材料PDF格式文件

卢尔君, 陶俊乾, 阳灿, 侯乙东, 张金水, 王心晨, 付贤智. 碳包覆Pd/TiO₂光催化产氢协同胺类选择性氧化合成亚胺[J]. 物理化学学报, 2023, 39(4), 2211029. doi: 10.3866/PKU.WHXB202211029

Erjun Lu, Junqian Tao, Can Yang, Yidong Hou, Jinshui Zhang, Xinchen Wang, Xianzhi Fu. Carbon-Encapsulated Pd/TiO₂ for Photocatalytic H₂ Evolution Integrated with Photodehydrogenative Coupling of Amines to Imines[J]. Acta Phys. -Chim. Sin. 2023, 39(4), 2211029. doi: 10.3866/PKU.WHXB202211029

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202211029

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I4/2211029

图/表 10

Scheme 1

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Table 1

Fig 7

Table 2

参考文献 58

1	Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, MNat. Mater2009,8,76. doi: 10.1038/nmat2317
2	Hisatomi, T.; Domen, KNat. Catal2019,2,387. doi: 10.1038/s41929-019-0242-6
3	Wang, Q.; Hisatomi, T.; Jia, Q. X.; Tokudome, H.; Pan, Z. H.; Takata, T.; Nakabayashi, M.; Shibata, N.; Kudo, A.; Yamada, T.; et alNat. Mater2016,15,611. doi: 10.1038/nmat4589
4	Li, Y. F.; Wu, Z. S.; Ma, Y. H.Acta Phys. -Chim. Sin2021,37,2009030.
	李云锋, 武占省, 马玉花物理化学学报,2021,37,2009030.
5	Zhang, J. S.; Wang, X. CAngew. Chem. Int. Ed2015,54,7230. doi: 10.1002/anie.201502659
6	Ledendecker, M.; Calderón, K.; Papp, C.; Steinrück, H. P.; Antonietti, M.; Shalom, MAngew. Chem. Int. Ed2015,54,12361. doi: 10.1002/anie.201502438
7	Mou, Q. X.; Wang, X. A.; Xu, Z. H.; Zul, P.; Li, E. L.; Zhao, P. P.; Liu, X. H.; Li, H. B.; Cheng, G. ZChin. Chem. Lett2022,33,562. doi: 10.1016/j.cclet.2021.08.028
8	Xia, B. Q.; Zhang, Y. Z.; Shi, B. Y.; Ran, J. R.; Davey, K.; Qiao, S. ZSmall Methods2020,4,2000063. doi: 10.1002/smtd.202000063
9	Biswal, B. P.; Vignolo-Gonzalez, H. A.; Banerjee, T.; Grunenberg, L.; Savasci, G.; Gottschling, K.; Nuss, J.; Ochsenfeld, C.; Lotsc, B. VJ. Am. Chem. Soc2019,141,11082. doi: 10.1021/jacs.9b03243
10	Chen, Y. J.; Ji, S. F.; Sun, W. M.; Lei, Y. P.; Wang, Q. C.; Li, A.; Chen, W. X.; Zhou, G.; Zhang, Z. D.; Wang, Y.; et alAngew. Chem. Int. Ed2020,59,1295. doi: 10.1002/anie.201912439
11	Zhao, X. X.; Feng, J. R.; Liu, J.; Shi, W.; Yang, G. M.; Wang, G. C.; Cheng, PAngew. Chem. Int. Ed2018,57,9790. doi: 10.1002/anie.201805425
12	Wang, T.; Tao, X. Q.; Li, X. L.; Zhang, K.; Liu, S. J.; Li, B. XSmall2021,17,2006255. doi: 10.1002/smll.202006255
13	Jiao, L.; Zhang, D. F.; Hao, Z. J.; Yu, F. H.; Lv, X. JACS Catal2021,11,8727. doi: 10.1021/acscatal.1c01520
14	Chai, Z. G.; Zeng, T. T.; Li, Q.; Lu, L. Q.; Xiao, W. J.; Xu, D. SJ. Am. Chem. Soc2016,138,10128. doi: 10.1021/jacs.6b06860
15	Li, D. X.; Yu, J. C. C.; Nguyen, V. H.; Wu, J. C. S.; Wang, X. XAppl. Catal. B-Environ2018,239,268. doi: 10.1016/j.apcatb.2018.08.010
16	Liu, J. F.; Zheng, X. Z.; Pan, L. L.; Fu, X. L.; Zhang, S. J.; Meng, S. G.; Chen, S. F.Appl. Catal. B-Environ.2021,298,120619. doi: 10.1016/j.apcatb.2021.120619
17	An, P.; Fu, Y.; Wei, D. L.; Guo, Y. L.; Zhan, W. C.; Zhang, J. S.Acta Phys. -Chim. Sin2021,37,2001025.
	安平, 付宇, 韦丹雷, 郭杨龙, 詹望成, 张金水物理化学学报,2021,37,2001025.
18	Tang, W. J.; Zhang, X. MChem. Rev2003,103,3029. doi: 10.1021/cr020049i
19	Huang, S. T.; Zhao, Z. J.; Wei, Z. Z.; Wang, M. X.; Chen, Y.; Wang, X. S.; Shao, F. G.; Zhong, X.; Li, X. N.; Wang, J. GGreen Chem2022,24,6945. doi: 10.1039/D2GC02161G
20	Chen, H.; Tang, T. H.; Malapit, C. A.; Lee, Y. S.; Prater, M. B.; Weliwatte, N. S.; Minteer, S. DJ. Am. Chem. Soc2022,144,4047. doi: 10.1021/jacs.1c13063
21	Tang, L.; Sun, H. Y.; Li, Y. F.; Zha, Z. G.; Wang, Z. YGreen Chem2012,14,3423. doi: 10.1039/C2GC36312G
22	Liu, H.; Xu, C. Y.; Li, D. D.; Jiang, H. LAngew. Chem. Int. Ed2018,57,5379. doi: 10.1002/anie.201800320
23	Huang, Y.; Liu, C. B.; Li, M. Y.; Li, H. Z.; Li, Y. W.; Su, R.; Zhang, BACS Catal2020,10,3904. doi: 10.1021/acscatal.0c00282
24	Yu, W. W.; Zhang, D.; Guo, X. W.; Song, C. S.; Zhao, Z. KCatal. Sci. Technol2018,8,5148. doi: 10.1039/C8CY01326H
25	Zou, J. H.; Zhou, W. H.; Huang, L. Q.; Guo, B. B.; Yang, C.; Hou, Y. D.; Zhang, J. S.; Wu, LJ. Catal2021,400,347. doi: 10.1016/j.jcat.2021.07.003
26	Bai, P.; Tong, X. L.; Gao, Y. Q.; Guo, P. FCatal. Sci. Technol2019,9,5803. doi: 10.1039/C9CY01311C
27	Chen, Y. J.; Sun, D.; Du, L. Z.; Jiao, Y. Z.; Han, W. Tian, G. HACS Appl. Mater. Interfaces2022,14,24425. doi: 10.1021/acsami.2c04826
28	Ohyama, J.; Yamamoto, A.; Teramura, K.; Shishido, T.; Tanaka, T.ACS Catal.2011,1,187. doi: 10.1021/cs100072k
29	Ma, M. J.; Wang, H. Q.; Liu, HChin. Chem. Lett2021,32,3613. doi: 10.1016/j.cclet.2021.04.012
30	Wenderich, K.; Mul, G. D.Chem. Rev.2016,116,14587. doi: 10.1021/acs.chemrev.6b00327
31	Du, X. H.; Li, Y.; Yin, H., Xiang, Q. J.Acta Phys. -Chim. Sin2018,34,414.
	杜新华, 李阳, 殷辉, 向全军物理化学学报,2018,34,414.
32	Yu, J.; Liu, Q.; Qiao, W.; Lv, D. D.; Li, Y. R.; Liu, C. B.; Yu, Y. F.; Li, Y. W.; Niemantsverdriet, H.; Zhang, B.; et alACS Catal2021,11,6656. doi: 10.1021/acscatal.1c01519
33	Wang, L. M.; Kobayashi, K.; Arisawa, M.; Saito, S.; Naka, HOrg. Lett2019,21,341. doi: 10.1021/acs.orglett.8b03271
34	Lu, E. J.; Wu, J. C.; Yang, B. Y.; Yu, D. X.; Yu, Z. Y.; Hou, Y. D.; Zhang, J. SACS Appl. Nano Mater2020,3,9192. doi: 10.1021/acsanm.0c01824
35	Yang, B. Y.; Zhang, S. K.; Gao, Y.; Huang, L. Q.; Yang, C.; Hou, Y. D.; Zhang, J. SAppl. Catal. B-Environ2022,304,120999. doi: 10.1016/j.apcatb.2021.120999
36	Zeng, L. D.; Liang, H. Y.; An, P.; Yu, D. X.; Yang, C.; Hou, Y. D.; Zhang, J. SAppl. Catal. A-Gen2022,633,118499. doi: 10.1016/j.apcata.2022.118499
37	Wei, Z. Z.; Chen, Y. Q.; Wang, J. Su, D. F.; Tang, M. H.; Mao, S. J.; Wang, YACS Catal2016,6,5816. doi: 10.1021/acscatal.6b01240
38	Zhan, W. C.; He, Q.; Liu, X. F.; Guo, Y. Q.; Wang, Y. Q.; Wang, L.; Guo, Y.; Borisevich, A. Y.; Zhang, J. S.; Lu, G. Z.; et alJ. Am. Chem. Soc2016,138,16130. doi: 10.1021/jacs.6b10472
39	Fronczak, M.; Kasprzak, A.; Bystrzejewski, MJ. Environ. Chem. Eng2021,9,104673. doi: 10.1016/j.jece.2020.104673
40	Jiao, Z. F.; Zhao, J. X.; Guo, X. N.; Tong, X. L.; Zhang, B.; Jin, G. Q.; Qin, Y.; Guo, X. YCatal. Sci. Technol2019,9,2266. doi: 10.1039/C9CY00353C
41	Li, J.; Zhang, L.; Li, J. W.; An, P.; Hou, Y. D.; Zhang, J. SACS Sustain. Chem. Eng2019,7,14023. doi: 10.1021/acssuschemeng.9b02529
42	Shiraishi, Y.; Hirakawa, H.; Togawa, Y.; Sugano, Y.; Ichikawa, S.; Hirai, TACS Catal2013,3,2318. doi: 10.1021/cs400532p
43	Zhang, J. S.; Qiao, Z. A.; Mahurin, S. M.; Jiang, X. G.; Chai, S. H.; Lu, H. F.; Nelson, K.; Dai, SAngew. Chem. Int. Ed2015,54,4582. doi: 10.1002/anie.201500305
44	Sun, X. M.; Gao, L.J. Acta Phys. -Chim. Sin2015,31,1521.
	孙雪梅, 高立军物理化学学报,2015,31,1521.
45	Naldoni, A.; Allieta, M.; Santangelo, S.; Marelli, M.; Fabbri, F.; Cappelli, S.; Bianchi, C. L.; Psaro, R.; Dal Santo, VJ. Am. Chem. Soc2012,134,7600. doi: 10.1021/ja3012676
46	Sasan, K.; Zuo, F.; Wang, Y.; Feng, P. YNanoscale2015,7,13369. doi: 10.1039/C5NR02974K
47	Zhou, H. R.; Yang, X. F.; Li, L.; Liu, X. Y.; Huang, Y. Q.; Pan, X. L.; Wang, A. Q.; Li, J.; Zhang, TACS Catal2016,6,1054. doi: 10.1021/acscatal.5b01933
48	Chen, H.; Yang, Z. Z.; Wang, X.; Polo-Garzon, F.; Halstenberg, P. W.; Wang, T.; Suo, X.; Yang, S. Z.; Meyer, H. M.; Wu, Z. L.; et alJ. Am. Chem. Soc2021,143,8521. doi: 10.1021/jacs.0c12817
49	Lu, E. J.; Zhang, Z. X.; Tao, J. Q.; Yu, Z. Y.; Hou, Y. D.; Zhang, J. SChem. Eur. J2022,28,e202201590. doi: 10.1002/chem.202201590
50	Lupan, O.; Postica, V.; Hoppe, M.; Wolff, N.; Polonskyi, O.; Pauporté, T.; Viana, B.; Majérus, O.; Kienle, L.; Faupel, F.; et alNanoscale2018,10,14107. doi: 10.1039/C8NR03260B
51	Zhao, J. R.; Fu, J. H.; Wang, J.; Tang, K. X.; Liu, Q.; Huang, J. HJ. Phys. Chem. C2022,126,15167. doi: 10.1021/acs.jpcc.2c03945
52	Zhou, H. R.; Yang, X. F.; Li, L.; Liu, X. Y.; Huang, Y. Q.; Pan, X. L.; Wang, A. Q.; Li, J.; Zhang, TACS Catal2016,6,1054. doi: 10.1021/acscatal.5b01933
53	Zhang, N.; Li, X. Y.; Liu, Y. F.; Long, R.; Li, M. Q.; Chen, S. G.; Qi, Z. M.; Wang, C. M.; Song, L. S.; Jiang, J. J.; et alSmall2017,13,1701354. doi: 10.1002/smll.201701354
54	Wang, H. T.; Yu, J. N.; Wei, S.; Lin, M. M.; Song, Y. J.; Wu, LChem. Eng. J2022,441,136020. doi: 10.1016/j.cej.2022.136020
55	Ma, R.; Yang, T. X.; Sun, J. H.; He, Y. F.; Feng, J. T.; Miller, J. T.; Li, D. QChem. Eng. Sci2019,210,115216. doi: 10.1016/j.ces.2019.115216
56	Zhang, B.; Yang, F.; Liu, H. C.; Yan, L. N.; Yang, W.; Xu, C.; Huang, S.; Li, Q.; Bao, W. J.; Liu, B.; et alInd. Eng. Chem. Res2019,58,19486. doi: 10.1021/acs.iecr.9b03619
57	Zhang, L. W.; Long, R.; Zhang, Y. M.; Duan, D. L.; Xiong, Y. J.; Zhang, Y. J.; Bi, Y. PAngew. Chem. Int. Ed2020,59,6224. doi: 10.1002/anie.201915774
58	Deng, Y.; Yan, W. J.; Guo, Y. J.; Wang, Q.; Bi, Y. P.; Dong, C.; Fan, L. FJ. Hazard. Mater2022,426,128107. doi: 10.1016/j.jhazmat.2021.128107


Entry	Catalyst	Con./%	Sel./% ^b	H₂ evolution/mmol
1	Pd/TiO₂	> 99	21	0.26
2 ^c	Pd/TiO₂	–	–	–
3	Pd/TiO₂@C-1	> 99	36.3	0.24
4	Pd/TiO₂@C-2	95	99	0.23
5 ^c	Pd/TiO₂@C-2	–	–	–
6	Pd/TiO₂@C-3	88	99	0.21
7 ^d	Pd/(TiO₂@C)	> 99	13.1	0.22
8 ^e	Pd/TiO₂-500	> 99	36	0.17
9 ^f	Pd/TiO₂*	97	16.2	0.26

[1]	陈轼逸, 付家龙, 裘建平, 常国菊, 郝仕油. 废弃医用口罩衍生的碳量子点增强BiOBr/g-C₃N₄ S型异质结光催化降解聚对苯二甲酸乙二醇酯(PET)[J]. 物理化学学报, 2026, 42(1): 100135 - .
[2]	黄火帅, 韦之栋, 严嘉玮, 池家晟, 苏千翔, 陈铭夏, 江治, 孙洋洲, 上官文峰. 揭示Zn_xCd_1−xS固溶体光催化析氢中的直接-间接带隙跃迁机制[J]. 物理化学学报, 2026, 42(1): 100141 - .
[3]	赵呈孝, 李昭霖, 吴东方, 杨小飞. SBA-15模板化共价三嗪框架增强光催化产氢[J]. 物理化学学报, 2026, 42(1): 100149 - .
[4]	陈芸, 邓代洁, 徐丽, 朱兴旺, 李赫楠, 孙成明. 共价键调控电荷转移以实现自供能电化学传感平台对重金属离子的灵敏分析[J]. 物理化学学报, 2026, 42(1): 100144 - .
[5]	张凤英, 梅杨林, 蒋毓蔓, 郑申申, 郑凯波, 周莹. 瞬态吸收光谱在太阳能转化利用中的研究进展[J]. 物理化学学报, 2025, 41(9): 100118 - .
[6]	王文龙, 郝文韬, 何浪, 乔佳, 李宁, 陈朝秋, 覃勇. 碳量子点/TiO₂ S型异质结的能带和吸附工程促进光催化CO₂甲烷化[J]. 物理化学学报, 2025, 41(9): 100116 - .
[7]	韦梦兰, 欧晓霞, 王艺濛, 张梦圆, 滕飞, 王凯旋. S型异质结g-C₃N₄/Bi₂WO₆高效降解左氧氟沙星：性能、机理及降解路径[J]. 物理化学学报, 2025, 41(9): 100105 - .
[8]	李静萍, 严素定, 吴佳曦, 程强, 王楷. LiFePO₄改善无机/有机S型光催化剂的过氧化氢光合作用[J]. 物理化学学报, 2025, 41(9): 100104 - .
[9]	吴琦, 王长华, 李莹莹, 张昕彤. 增强g-C₃N₄@BN范德华异质结界面上的三重态电子转移增强光催化合成H₂O₂[J]. 物理化学学报, 2025, 41(9): 100107 - .
[10]	蔡家杰, 程畅, 刘博文, 张建军, 姜传佳, 程蓓. CdS/DBTSO-BDTO S型异质结光催化制氢及其电荷转移动力学[J]. 物理化学学报, 2025, 41(8): 100084 - .
[11]	袁乐汪, 彭垚垚, 管宗杰, 方煜. 二维共价有机框架作为光催化剂在有机合成中的研究进展[J]. 物理化学学报, 2025, 41(8): 100086 - .
[12]	刘方璇, 刘子妍, 周国伟, 高婷婷, 刘文宇, 孙彬. 中空结构光催化剂[J]. 物理化学学报, 2025, 41(7): 100071 - .
[13]	王玉, 石海洋, 陈子涵, 陈峰, 王苹, 王雪飞. 具有富电子Pt^δ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性[J]. 物理化学学报, 2025, 41(7): 100081 - .
[14]	罗雅丹, 郑浩, 李鑫, 李锋民, 唐华, 佘希林. 调节O, S共掺杂C₃N₄中的活性氧生成以促进光催化降解微塑料[J]. 物理化学学报, 2025, 41(6): 100052 - .
[15]	宋相海, 刘晓颖, 任智祥, 刘想, 汪梅, 吴元锋, 周伟强, 朱志, 霍鹏伟. 氮掺杂显著提升BiOBr光催化还原CO₂性能研究[J]. 物理化学学报, 2025, 41(6): 100055 - .

碳包覆Pd/TiO₂光催化产氢协同胺类选择性氧化合成亚胺

Carbon-Encapsulated Pd/TiO₂ for Photocatalytic H₂ Evolution Integrated with Photodehydrogenative Coupling of Amines to Imines

RichHTML

PDF

赞

可视化

摘要/Abstract

支持信息

引用本文

使用本文

图/表 10

参考文献 58

相关文章 15

Metrics

推荐阅读 0