高稳定性的氮掺杂氧化钽光催化甲醇C-H活化和直接C-C偶联制乙二醇

doi:10.1016/S1872-2067(21)63797-X

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1459-1467.DOI: 10.1016/S1872-2067(21)63797-X

高稳定性的氮掺杂氧化钽光催化甲醇C-H活化和直接C-C偶联制乙二醇

王力梅^a^,^b, 杜大学^a, 张彪^b, 谢顺吉^b^,^*(), 张庆红^b, 王海燕^a^,^#(), 王野^b^,^$()

^a燕山大学环境与化学工程学院,河北省应用化学重点实验室,河北秦皇岛066004
^b厦门大学化学化工学院, 固体表面物理化学国家重点实验室, 能源材料化学协同创新中心, 醇醚酯化工清洁生产国家工程实验室, 福建厦门361005

收稿日期:2021-01-16 接受日期:2021-03-03 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 谢顺吉,王海燕,王野
基金资助:
国家自然科学基金(22022201);国家自然科学基金(21972115)

Solar energy-driven C-H activation of methanol for direct C-C coupling to ethylene glycol with high stability by nitrogen doped tantalum oxide

Limei Wang^a^,^b, Daxue Du^a, Biao Zhang^b, Shunji Xie^b^,^*(), Qinghong Zhang^b, Haiyan Wang^a^,^#(), Ye Wang^b^,^$()

^aKey Laboratory of Applied Chemistry of Hebei Province, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China
^bState Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2021-01-16 Accepted:2021-03-03 Online:2021-09-18 Published:2021-05-16
Contact: Shunji Xie,Haiyan Wang,Ye Wang
About author:^$ E-mail: wangye@xmu.edu.cn
^# E-mail: hywang@ysu.edu.cn;
^* E-mail: shunji_xie@xmu.edu.cn;
Supported by:
National Natural Science Foundation of China(22022201);National Natural Science Foundation of China(21972115)

摘要/Abstract

摘要：

乙二醇是非常重要的基础化学品, 不仅可以作为合成聚合物(如聚对苯二甲酸乙二醇酯)的重要单体,也可以用作防冻剂和燃料添加剂等, 具有广泛的用途. 乙二醇的年产量超过2500万吨, 目前主要的工业合成路线是由石油衍生的乙烯通过环氧化制环氧乙烷, 环氧乙烷再水解制乙二醇. 甲醇是一种清洁的平台化合物, 不仅可以由天然气和煤炭通过传统的合成气过程生产, 也可以由生物质和CO₂直接合成. 直接以甲醇为原料是合成乙二醇的理想过程, 但目前热催化还未实现该过程. 通过太阳能驱动的C-H活化和C-C偶联过程, 可以实现甲醇直接偶联制乙二醇的理想反应过程. 光催化甲醇制乙二醇可以在十分温和的条件下进行, 目前已报道的甲醇制乙二醇光催化剂均为硫化物半导体材料, 如CdS, ZnS和Zn₂In₂S₅, 但硫化物存在的光腐蚀和毒性等问题迫使我们去发展一种更加稳定和环境友好的光催化剂. 氧化物基半导体材料, 如Ta₂O₅, TiO₂, ZnO和WO₃等, 是一类相对硫化物半导体材料更加稳定的光催化材料, 然而目前还没有氧化物基半导体光催化剂用于光催化甲醇制乙二醇的报道.
本文率先将金属氧化物光催化剂Ta₂O₅, 用于甲醇制乙二醇的光催化反应, 实现了乙二醇的选择性合成. 在单纯的Ta₂O₅催化剂上, 乙二醇选择性可达73%. Ta₂O₅十分独特, 可以实现甲醇的光催化C-C偶联制乙二醇, 而其他金属氧化物光催化剂(如TiO₂, ZnO, WO₃和Nb₂O₅)光催化转化甲醇只生成甲醛和甲酸等C1产物. 进一步通过简单、方便的氨气焙烧法, 制备了一系列不同氮掺杂量的氧化钽(N-Ta₂O₅)催化剂. 在未经助催化剂修饰的氮含量为2.3%的2%N-Ta₂O₅光催化剂上, 乙二醇选择性为71%, 生成速率可达4.0 mmol g_cat^-1 h^-1, 约为Ta₂O₅的9倍, 同时显著高于已报道的未经助催化剂修饰的CdS催化剂性能. 通过光电流、表面光电压谱和理论计算等方法系统地研究了氮掺杂氧化钽具有高的光催化甲醇制乙二醇性能的重要原因, 发现氮掺杂氧化钽高的电荷分离能力是决定其具有高活性的关键因素. 另一方面, 氮掺杂氧化钽表现出了非常高的反应稳定性, 在超过160 h的循环测试过程中, 乙二醇的生成速率基本保持不变, 这是目前已报道的金属硫化物光催化剂所未能实现的. 在长达60 h的反应过程中, 未经助催化剂修饰的2%N-Ta₂O₅催化剂上乙二醇生成量基本随时间线性增长, 收率可达3.6%. 进一步研究发现, 钽基半导体材料(Ta₂O₅和N-Ta₂O₅)可以在保持甲醇羟基不变的情况下优先活化甲醇C-H键, 生成羟甲基自由基(•CH₂OH), 随后羟甲基自由基经C-C偶联生成乙二醇. 钽基半导体光催化剂是一种环境友好且十分稳定的甲醇光催化偶联制乙二醇的优异催化剂, 未来基于该类催化剂不仅有希望发展出更加高效、稳定的甲醇制乙二醇光催化剂, 还有希望为更广的羟基存在下的C-H键选择性活化反应过程设计高效稳定的催化剂提供借鉴和指导.

关键词: 甲醇, C-H活化, C-C偶联, 乙二醇, 钽基光催化剂

Abstract:

Direct photocatalytic coupling of methanol to ethylene glycol (EG) is highly attractive. The reported photocatalysts for this reaction are all metal sulfide semiconductors, which may suffer from photocorrosion and have low stability. Thus, the development of non-sulﬁde photocatalysts for efficient photocatalytic coupling of methanol to EG and H₂ with high stability is urgent but extremely challenging. Herein, the first metal oxide photocatalyst, tantalum-based semiconductor, is reported for preferential activation of C-H bond within methanol to form hydroxymethyl radical (•CH₂OH) and subsequent C-C coupling to EG. Compared with other metal oxide photocatalysts, such as TiO₂, ZnO, WO₃, Nb₂O₅, tantalum oxide (Ta₂O₅) is unique in that it can realize the selective photocatalytic coupling of methanol to EG. The co-catalyst free nitrogen doped tantalum oxide (2%N-Ta₂O₅) shows an EG formation rate as high as 4.0 mmol g_cat^-1 h^-1, about 9 times higher than that of Ta₂O₅, with a selectivity higher than 70%. The high charge separation ability of nitrogen doped tantalum oxide plays a key role in its high activity for EG production. This catalyst also shows excellent stability longer than 160 h, which has not been achieved over the reported metal sulfide photocatalysts. Tantalum-based photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.

Key words: Methanol, C-H activation, C-C coupling, Ethylene glycol, Tantalum-based photocatalyst

王力梅, 杜大学, 张彪, 谢顺吉, 张庆红, 王海燕, 王野. 高稳定性的氮掺杂氧化钽光催化甲醇C-H活化和直接C-C偶联制乙二醇[J]. 催化学报, 2021, 42(9): 1459-1467.

Limei Wang, Daxue Du, Biao Zhang, Shunji Xie, Qinghong Zhang, Haiyan Wang, Ye Wang. Solar energy-driven C-H activation of methanol for direct C-C coupling to ethylene glycol with high stability by nitrogen doped tantalum oxide[J]. Chinese Journal of Catalysis, 2021, 42(9): 1459-1467.

×
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)63797-X

https://www.cjcatal.com/CN/Y2021/V42/I9/1459

图/表 8

Fig. 1. (a) Schematic illustration for the synthesis of N-Ta2O5. SEM images of Ta2O5 (b), 0.6%N-Ta2O5 (c), 2%N-Ta2O5 (d), and 7%N-Ta2O5 (e); (f) EDX mapping and element distributions of 2%N-Ta2O5.

Fig. 2. XRD patterns (a) and Raman spectra (b) of Ta2O5 and N-Ta2O5; N 1s (c), and (d) Ta 4f XPS spectra of Ta2O5 and N-Ta2O5.

Fig. 3. (a) UV-Vis diffuse reflectance spectra of Ta2O5 and N-Ta2O5; (b) The corresponding plots of modified Kubelka-Munk function versus the energy of exciting light of Ta2O5 and N-Ta2O5; (c) Energy levels of several related redox couples and band-edge positions of Ta2O5 and N-Ta2O5.

Table 1 Photocatalytic performances of Ta2O5, N-Ta2O5 and some typical metal oxide photocatalysts for the MTEG reaction.

Catalyst	Formation rate (mmol g_cat^-1 h^-1)						e^-/h^{+ a}	Selectivity ^b (%)
Catalyst	EG	HCHO	HCOOH	CO	CO₂	H₂	e^-/h^{+ a}	EG	HCHO	HCOOH
Ta₂O₅	0.43	0.26	0	0	0	0.58	1.09	73	27	0
0.6%N-Ta₂O₅	2.0	2.4	0.01	0	0	4.3	0.96	62	37	1
2%N-Ta₂O₅	4.0	3.2	0.10	0	0	8.7	1.06	71	28	1
7%N-Ta₂O₅	0.2	0.13	0	0	0	0.27	0.93	76	24	0
TiO₂	0	1.6	0.11	0.16	0.042	2.0	0.91	0	84	5.6
ZnO	0	3.0	0.038	0.23	0.028	3.1	0.90	0	91	1.2
WO₃	0	0.48	0.051	0	0	0.23	0.94	0	99	1
Nb₂O₅	0	1.4	0.071	0	0	0.8	1.1	0	99	1

Fig. 4. (a) Time course process of 2%N-Ta2O5 in MTEG reaction within 12 h. (b) The product formation rate of 2%N-Ta2O5 in repeated use within 14 cycles (12 h for each cycle). (c) Quantum yields of EG at different wavelengths and UV-Vis diffuse reflectance spectrum of 2%N-Ta2O5. (d) Photocatalytic performances of 2%N-Ta2O5 in 60 h. Reaction conditions: catalyst, 10 mg; solution, 4.0 mL CH3OH (76 wt%) + 1.0 mL H2O (24 wt%), 5.0 mL; N2 atmosphere; 300 W Xe lamp as light source.

Fig. 5. (a) Transient photocurrent responses of Ta2O5 and N-Ta2O5; (b) SPV spectra of Ta2O5 and N-Ta2O5.

Fig. 6. (a) Electron density differences of the top view for Ta2O5 (left) and N-Ta2O5 (right) models. Iso-surface value is 0.004 e?-3. Yellow and blue contours represent electron accumulation and depletion, respectively. (b) Calculated TDOS for Ta2O5 and N-Ta2O5 models.

Fig. 7. (a) In situ ESR spectra of systems containing Ta2O5 and N-Ta2O5 catalysts in aqueous methanol solutions in the presence of DMPO (a spin-trapping agent) without or with light irradiation; (b) Illustration of the photocatalytic coupling of methanol to EG over N-Ta2O5 catalyst.

参考文献

[1]	G. Ciamician, Science, 1912,36, 385-394.
[2]	H. Kisch, Angew. Chem. Int. Ed., 2013,52, 812-847.
[3]	S. Y. Zhang, F. M. Zhang, Y. Q Tu, Chem. Soc. Rev., 2011,40, 1937-1949.
[4]	M. Fagnoni, D. Dondi, D. Ravelli, A. Albini, Chem. Rev., 2007,107, 2725-2756.
[5]	S. J Xie, W. C. Ma, X. J. Wu, H. K. Zhang, Q. H. Zhang, Y. D. Wang, Y. Wang, Energy Environ. Sci., 2021,14, 37-89.
[6]	Q. Guo, F. Liang, X. B. Li, Y. J Gao, M. Y. Huang, Y. Wang, S. Xia, X. G. Gao, Q. C. Gan, Z. S. Lin, C. H. Tung, L. Z. Wu, Chem, 2019,5, 2605-2616.
[7]	X. J. Cui, R. Huang, D. H. Deng, EnergyChem, 2021,3, 100050.
[8]	J. H. Tang, Y. Z. Sun, Mater. Adv., 2020,1, 2155-2162.
[9]	B. Q. Xia, Y. Z. Zhang, B. Y. Shi, J. R. Ran, K. Davey, S. Qiao, Small Methods, 2020,4, 2000063.
[10]	Y. F. Zhao, W. Gao, S. W. Li, G. R. Williams, A. H. Mahadi, D. Ma, Joule, 2019,3, 920-937.
[11]	P. Duan, H. Zhang, S. Xie, Q. Zhang, Y. Wang, J. Xiamen Univ. (Nat. Sci.), 2020,59, 630-639.
[12]	S. Yanagida, T. Azuma, H. Kawakami, H. Kizumoto, H. Sakurai, J. Chem. Soc., Chem. Commun., 1984,1, 21-22.
[13]	S. J. Xie, Z. B. Shen, J. Deng, P. Guo, Q. H. Zhang, H. K. Zhang, C. Ma, Z. Jiang, J. Cheng, D. Deng, Y. Wang, Nat. Commun., 2018,9, 1181.
[14]	H. K. Zhang, S. J. Xie, J. Y. Hu, J. X. Wu, Q. U. Zhang, J. Cheng, Y. Wang, Chem. Commun., 2020,56, 1776-1779.
[15]	J. L. Gong, J. Energy Chem., 2018,27, 949-950.
[16]	Y. H. Fan, J. X. Bao, L. Shi, S. S.Li, Y. W. Lu, H. J. Liu, H. Wang, L. S. Zhong, Y. H. Sun, Catal. Lett., 2018,148, 2274-2282.
[17]	H. R. Yue, Y. J. Zhao, X. B. Ma, J. L. Gong, Chem. Soc. Rev., 2012,41, 4218-4244.
[18]	M. Y. Zheng, J. F. Pang, R. Y. Sun, A. Q. Wang, T. Zhang, ACS Catal., 2017,7, 1939-1954.
[19]	Z. B. Shen, S. J. Xie, W. Q. Fan, Q. H. Zhang, Z. K. Xie, W. M. Yang, Y. D. Wang, J. C. Lin, X. J. Wu, H. L. Wan, Y. Wang, Catal. Sci. Technol., 2016,6, 6485-6489.
[20]	S. J. Xie, Z. B. Shen, H. M. Zhang, J. Cheng, Q. H. Zhang, Y. Wang, Catal. Sci. Technol., 2017,7, 923-933.
[21]	S. Heyuan, J. Ronghua, K. Meirong, C. Jing, Chin. J. Catal., 2013,34, 1035-1050.
[22]	G. A. Olah, Angew. Chem. Int. Ed., 2013,52, 104-107.
[23]	M. Wang, M. J. Liu, J. M. Lu, F. Wang, Nat. Commun., 2020,11, 1083.
[24]	X. B. Chen, S. H. Shen, L. J. Guo, S. S. Mao, Chem. Rev., 2010,110, 6503-6570.
[25]	J. Y. Li, Y. H. Li, M. Y. Qi, Q. Lin, Z. R. Tang, Y. J. Xu, ACS Catal., 2020,10, 6262-6280.
[26]	K. Li, D. Martin, J. Tang, Chin. J. Catal., 2011,32, 879-890.
[27]	S. S. Chen, Y. Qi, C. Li, K. Domen, F. X. Zhang, Joule, 2018,2, 2260-2288.
[28]	G. B. Chen, Geoffrey I. Waterhouse, R. Shi, J. Q. Zhao, Z. H. Li, L. Z. Wu, C. H. Tung, T. R. Zhang, Angew. Chem. Int. Ed., 2019,58, 17528-17551.
[29]	Q. Guo, T.K. Minton, X. Yang, Chin. J. Catal., 2015,36, 1649-1655.
[30]	Y. Ma, X. Wang, C. Li, Chin. J. Catal., 2015,36, 1519-1527.
[31]	S. Xie, H. Zhang, G. Liu, X. Wu, J. Lin, Q. Zhang, Y. Wang, Chin. J. Catal., 2020,41, 1125-1131.
[32]	P. Zhang, J. Zhang, J. Gong, Chem. Soc. Rev., 2014,43, 4395-4422.
[33]	L. Pei, Y. J. Yuan, W. F. Bai, T. Z. Li, H. Zhu, Z. F. Ma, J. S. Zhong, S. C. Yan, Z. G. Zou, ACS Catal., 2020,10, 15083-15091.
[34]	T.M. Suzuki, S. Saeki, K. Sekizawa, K. Kitazumi, N. Takahashi, T. Morikawa, Appl. Catal. B, 2017,202, 597-604.
[35]	H. Sakamoto, T. Ohara, N. Yasumoto, Y. Shiraishi, S. Ichikawa, S. Tanaka, T. Hirai, J. Am. Chem. Soc., 2015,137, 9324-9332.
[36]	S. Naveenraj, G. Lee, S. Anandan, J.J. Wu, Mater. Res. Bull., 2015,67, 20-46.
[37]	M. Liu, W. You, Z. Lei, T. Takata, K. Domen, C. Li, Chin. J. Catal., 2006,27, 556-558.
[38]	B. Hammer, L.B. Hansen, J.K. Noørskov, Phys. Rev. B, 1999,59, 7413-7421.
[39]	G. Kresse, J. Hafner, Phys. Rev. B, 1993,47, 558-561.
[40]	E. Nurlaela, M. Harb, S. Gobbo, M. Vashishta, K. Takanabe, J. Solid State Chem., 2015,229, 219-227.
[41]	S. Bae, H. Shin, S. Lee, D. Kim, H. Jung, K. Hong, React. Kinet. Mech. Catal., 2012,106, 67-81.
[42]	W. S. Liu, S. H. Huanga, C. F. Liua, C. W. Hu, T. Y. Chen, T. P. Perng, Appl. Surf. Sci., 2018,459, 477-482.
[43]	E. Nurlaela, S. Ould-Chikh, M. Harb, S. Gobbo, M. Aouine, E. Puzenat, P. Sautet, K. Domen, J. Basset, K. Takanabe, Chem. Mater., 2014,26, 4812-4825.
[44]	W. D. K. Clark, N. Sutin, J. Am. Chem. Soc., 1977,99 4676-4682.
[45]	L. J. Zhang, B. Hou, A. Wang, Z. Li, H. Wang, T. Zhang, AIChE J., 2015,61, 224-238.
[46]	T. U. Chae, S. Y. Choi, J. Y. Ryu, S. Y. Lee, AIChE J., 2018,64, 4193-4200.
[47]	L. Zhang, S. Li, B. Liu, D. Wang, T. Xie, ACS Catal., 2014,4, 3724-3729.
[48]	L. L. Bi, D. D. Xu, L. T. Zhang, Y. T. Lin, D. J. Wang, T. F. Xie, Phys. Chem. Chem. Phys., 2015,17, 29899-29905.
[49]	L. L. Bi, X. P. Gao, L. J. Zhang, D. J. Wang, X. X. Zou, T. F. Xie, ChemSusChem, 2018,11, 276-284.

高稳定性的氮掺杂氧化钽光催化甲醇C-H活化和直接C-C偶联制乙二醇

Solar energy-driven C-H activation of methanol for direct C-C coupling to ethylene glycol with high stability by nitrogen doped tantalum oxide

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]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[2]	乔蔚, 于立策, 常进法, 杨甫林, 冯立纲. MoSe₂纳米片耦合Pt纳米颗粒用于高效双功能催化甲醇辅助水电解制氢[J]. 催化学报, 2023, 51(8): 113-123.
[3]	程璐, 陈许宁, 胡培君, 曹宵鸣. 双氧水对于单核铜分子筛催化甲烷直接氧化制甲醇反应性能的利弊[J]. 催化学报, 2023, 51(8): 135-144.
[4]	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.
[5]	孟帅奇, 李忠玉, 张鹏, Francisca Contreras, 季宇, Ulrich Schwaneberg. 深度学习指导的热裂褐藻角质酶工程用于促进PET解聚[J]. 催化学报, 2023, 50(7): 229-238.
[6]	刘润泽, 邵雪, 王畅, 戴卫理, 关乃佳. 甲醇制烃反应机理: 基础及应用研究[J]. 催化学报, 2023, 47(4): 67-92.
[7]	刘玥, 章伟, 刘海超. 三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态[J]. 催化学报, 2023, 46(3): 56-63.
[8]	禹伟, 高教琪, 姚伦, 周雍进. 多形汉逊酵母细胞工厂实现甲醇生物转化合成3-羟基丙酸[J]. 催化学报, 2023, 46(3): 84-90.
[9]	林杉帆, 郅玉春, 张文娜, 袁小帅, 张成伟, 叶茂, 徐舒涛, 魏迎旭, 刘中民. 氢转移反应对分子筛催化甲醇和二甲醚动态自催化反应历程的贡献: 深入理解甲醛的生成机理和作用机制[J]. 催化学报, 2023, 46(3): 11-27.
[10]	沙峰, 唐珊, 汤驰洲, 冯振东, 王集杰, 李灿. ZnZrO_x固溶体催化剂表面羟基在CO₂加氢制甲醇中的作用[J]. 催化学报, 2023, 45(2): 162-173.
[11]	李跃辉, 司端惠, 王旺银, 薛松, 商文喆, 迟占有, 李灿, 郝策, Govindjee Govindjee, 史彦涛. 光系统II光驱动CO₂同化的光合作用[J]. 催化学报, 2023, 44(1): 117-126.
[12]	王冶, 韩晶峰, 王男, 李冰, 杨淼, 吴一墨, 江子潇, 魏迎旭, 田鹏, 刘中民. SAPO-14催化的甲醇制丙烯反应: 反应机理与失活[J]. 催化学报, 2022, 43(8): 2259-2269.
[13]	Chuncheng Liu, Evgeny A. Uslamin, Sophie H. van Vreeswijk, Irina Yarulina, Swapna Ganapathy, Bert M. Weckhuysen, Freek Kapteijn, Evgeny A. Pidko. MFI/MEL分子筛催化甲醇制烯烃反应关键参数的集成方法[J]. 催化学报, 2022, 43(7): 1879-1893.
[14]	李垒, 欧阳汶俊, 郑泽锋, 叶凯航, 郭禹希, 秦延林, 伍珍珍, 林展, 王铁军, 张山青. 基于Pt@TiO₂催化剂光-热协同催化甲醇-水液相重整甲醇制氢[J]. 催化学报, 2022, 43(5): 1258-1266.
[15]	王旺银. 从液态阳光人工光合成淀粉[J]. 催化学报, 2022, 43(4): 895-897.