共价三嗪框架复合Co单活性位点光催化制合成气

doi:10.1016/S1872-2067(20)63603-8

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 123-130.DOI: 10.1016/S1872-2067(20)63603-8

共价三嗪框架复合Co单活性位点光催化制合成气

何亚军, 陈鑫, 黄驰, 李留义^*(), 杨程凯, 于岩^#()

福州大学材料科学与工程学院, 生态材料先进技术重点实验室, 福建福州350108

收稿日期:2020-02-26 接受日期:2020-04-10 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 李留义,于岩
基金资助:
国家自然科学基金(U1905215);国家自然科学基金(51672046);福建省自然科学基金(2019J01226);能源与环境光催化国家重点实验室开放课题(SKLPEE-KF201815)

Encapsulation of Co single sites in covalent triazine frameworks for photocatalytic production of syngas

Yajun He, Xin Chen, Chi Huang, Liuyi Li^*(), Chengkai Yang, Yan Yu^#()

Key Laboratory of Eco-materials Advanced Technology, College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, Fujian, China

Received:2020-02-26 Accepted:2020-04-10 Online:2021-01-18 Published:2021-01-18
Contact: Liuyi Li,Yan Yu
About author:^#E-mail: yuyan@fzu.edu.cn
^*E-mail: lyli@fzu.edu.cn;
Supported by:
National Natural Science Foundation of China(U1905215);National Natural Science Foundation of China(51672046);Natural Science Foundation of Fujian Province of China(2019J01226);Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(SKLPEE-KF201815)

摘要/Abstract

摘要：

合成气是费托合成的关键原料, 目前其主要是通过天然气重整或煤气化来制备, 但是该制备过程需要苛刻的合成条件. 光催化技术利用太阳能将CO₂还原制备合成气是未来能源开发的重要研究方向. 到目前为止, 已经开发了许多用于生产合成气的光催化系统. 然而, 大多数催化体系使用昂贵的金属如Re和Ru作为光敏剂和或催化剂, 利用非贵金属催化剂光催化还原CO₂制合成气是实现环境可持续发展的一种有效方法. 共价三嗪框架(CTF)由于具有可调节的光吸收性质、在分子水平上可调节的电子结构、高表面积和富氮结构, 因而在光催化体系中具有明显优势. 在此, 我们设计了一种基于分子内异质结的CTF光催化CO₂还原生成合成气体系, 通过傅里叶变换红外光谱(FT-IR)、核磁共振波谱(NMR)和X射线光电子能谱(XPS)等表征证明了CTF内的分子内异质结, 采用X射线多晶衍射(XRD)、比表面积及孔隙度分析(BET)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和紫外-可见吸收光谱(UV-Vis DRS)等表征手段充分研究了CTF的组成、结构与光学性质. 将所制备的CTF光催化剂应用于可见光催化还原CO₂反应中, 实验结果表明, 基于分子内异质结的CTF在10 h内达到 3303 μmol g^-1(CO:H₂ = 1.4:1)的合成气产率, 相对于不具有分子内异质结的CTF催化体系, 产率提高了3倍. 时间分辨荧光发射衰减光谱、荧光光谱和瞬时光电流图谱等测试结果表明, 分子内异质结极大提高了CTF内光生载流子的空间分离和转移效率. 反应体系中自组装形成的吡啶Co配合物作为Co单活性位点可有效吸附和配位活化CO₂分子. 理论计算进一步证明含有分子内异质结结构的CTF能极大地促进电荷分离效率, 从而实现催化性能的增强. 这项工作不仅显示了CTF在光催化等领域潜在的应用前景, 而且为合理设计基于CTF的光催化体系提供了新的见解.

关键词: 合成气, 光催化, 共价三嗪框架, 二氧化碳还原, 单点催化剂, 合成气

Abstract:

The photocatalytic production of syngas using a noble-metal-free catalytic system is a promising approach for renewable energy and environmental sustainability. In this study, we demonstrate an efficient catalytic system formed by integrating Co single sites, which act as the active sites, in covalent triazine frameworks (CTFs), which act as the photoabsorber, for the photocatalytic production of syngas from CO₂ in aqueous solution. The enhanced light absorption of the CTFs, which contain intramolecular heterojunctions, in conjunction with 0.8 mmol L^-1 of the Co complex enables excellent syngas production with a yield of 3303 μmol g ^-1 (CO:H₂= 1.4:1) in 10 h, which is about three times greater than that achieved using CTF without a heterojunction. In the photocatalytic reaction, the coordinated single Co centers accept the photogenerated electrons from the CTF, and serve as active sites for CO₂ conversion through an adsorption-activation-reaction mechanism. Theoretical calculations further reveal that the intramolecular heterojunctions highly promote photogenerated charge separation, thus boosting photocatalytic syngas production. This work reveals the promising potential of CTFs for single-metal-site-based photocatalysis.

Key words: Photocatalysis, Covalent triazine frameworks, CO₂ reduction, Single site, Syngas

何亚军, 陈鑫, 黄驰, 李留义, 杨程凯, 于岩. 共价三嗪框架复合Co单活性位点光催化制合成气[J]. 催化学报, 2021, 42(1): 123-130.

Yajun He, Xin Chen, Chi Huang, Liuyi Li, Chengkai Yang, Yan Yu. Encapsulation of Co single sites in covalent triazine frameworks for photocatalytic production of syngas[J]. Chinese Journal of Catalysis, 2021, 42(1): 123-130.

×
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)63603-8

https://www.cjcatal.com/CN/Y2021/V42/I1/123

图/表 7

Fig. 1. Schematic of the synthesis of CTF-TPN and CTF-TDPN and their application in the photocatalytic reduction of CO2 under visible light.

Fig. 2. (a) FTIR spectra of the monomers and CTFs; (b) Solid state 13C NMR spectra, (c) N 1s XPS profiles, and (d) XRD patterns of CTF-TPN and CTF-TDPN.

Fig. 3. (a) N2 adsorption-desorption isotherms at 77 K (inset: pore size distribution); (b) CO2 adsorption-desorption isotherms at 273 K (inset: isotherms of the heat of adsorption for CO2) of CTF-TPN and CTF-TDPN; (c) TEM image of CTF-TDPN; (d) UV-vis DRS spectra; (e) band gaps of the CTFs; (f) band structures of the CTFs.

Fig. 4. Photocatalytic evolution of CO and H2 by (a) CTF-TPN and (b) CTF-TDPN; (c) comparison of the average CO and H2 evolution efficiencies of the CTFs; (d) control experiments using CTF-TDPN; (e) experiments using different solvents; (f) experiments with different H2O contents in the reaction. MeCN, DMF, DMC, and Diox are acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and 1,4-dioxane, respectively.

Fig. 5. (a) TEM image and (b) EDX mapping of the recovered CTF-TDPN.

Fig. 6. (a) PL spectra under 365 nm excitation at room temperature (Inset: CTFs under 365 nm UV-light); (b) time-resolved fluorescence emission decay spectra; (c) transient photocurrents under visible light (≥ 420 nm) irradiation of CTF-TPN, CTF-TDPN, and CTF-HUST-1; (d) UV-vis absorption spectra of [Co(bpy)3]2+ formed in situ by the consecutive addition of bpy to Co(OAc)2?4H2O in MeCN/H2O (ν/ν = 3:1); (e) CV curves of the self-assembled [Co(bpy)3]2+ under Ar and CO2 atmospheres; (f) PL spectra of CTF-TDPN with [Co(bpy)3]2+ in MeCN/H2O upon irradiation at 365 nm.

Fig. 7. HOMOs and LUMOs of (a) CTF-TPN and (b) CTF-HUST-1; ESP maps of (c) CTF-TPN and (d) CTF-HUST-1; (e) proposed mechanism for the photocatalytic syngas production with [Co(bpy)3]2+ as a catalyst under visible light irradiation.

参考文献

[1]	Y. F. Zhao, G. I. N. Waterhouse, G. B. Chen, X. Y. Xiong, L. Z. Wu, C. H. Tung, T. R. Zhang, Chem. Soc. Rev., 2019, 48, 1972-2010.
[2]	X. Li, J. Yu, M. Jaroniec, X. Chen, Chem. Rev., 2019, 119, 3962-4179.
[3]	J. M. Spurgeon, B. Kumar, Energy Environ. Sci., 2018, 11, 1536-1551.
[4]	M. D. Porosoff, B. H. Yan, J. G. Chen, Energy Environ. Sci., 2016, 9, 62-73.
[5]	H. Wang, Y. Wang, L. Guo, X. Zhang, C. Ribeiro, T. He, Chin. J. Catal., 2020, 41, 131-139.
[6]	M. Liu, Y. F. Mu, S. Yao, S. Guo, X. W. Guo, Z. M. Zhang, T. B. Lu, Appl. Catal. B, 2019, 245, 496-501.
[7]	J. C. Hu, M. X. Gui, W. Xia, J. Wu, Y. N. Zhou, N. D. Feng, J. W. Xiao, H. F. Liu, C. H. Tung, L. Z. Wu, F. Wang, J. Mater. Chem. A, 2019, 7, 10475-10482.
[8]	J. S. Lee, D. I. Won, W. J. Jung, H. J. Son, C. Pac, S. O. Kang, Angew. Chem. Int. Ed., 2017, 56, 976-980.
[9]	A. Li, T. Wang, X. Chang, Z. J. Zhao, C. Li, Z. Huang, P. Yang, G. Zhou, J. Gong, Chem. Sci., 2018, 9, 5334-5340.
[10]	M. Liu, S. Wageh, A. A. Al-Ghamdi, P. Xia, B. Cheng, L. Zhang, J. Yu, Chem. Commun., 2019, 55, 14023-14026.
[11]	X. Li, C. Liu, D. Wu, J. Li, P. Huo, H. Wang, Chin. J. Catal., 2019, 40, 928-939.
[12]	J. Low, B. Dai, T. Tong, C. Jiang, J. Yu, Adv. Mater., 2019, 31, 1802981.
[13]	J. Jiang, S. Cao, C. Hu, C. Chen, Chin. J. Catal., 2017, 38, 1981-1989.
[14]	B. P. Biswal, H. A. Vignolo-González, T. Banerjee, L. Grunenberg, G. Savasci, K. Gottschling, J. Nuss, C. Ochsenfeld, B. V. Lotsch, J. Am. Chem. Soc., 2019, 141, 11082-11092.
[15]	W. Zhong, R. Sa, L. Li, Y. He, L. Li, J. Bi, Z. Zhuang, Y. Yu, Z. Zou, J. Am. Chem. Soc., 2019, 141, 7615-7621.
[16]	W. T. Eckenhoff, Coord. Chem. Rev. , 2018, 373, 295-316.
[17]	J. W. Wang, W. J. Liu, D. C. Zhong, T. B. Lu, Coord. Chem. Rev., 2019, 378, 237-261.
[18]	J. Xiao, W. Yang, S. Gao, C. Sun, Q. Li, J. Mater. Sci. Technol., 2018, 34, 2331-2336.
[19]	C. Bie, B. Zhu, F. Xu, L. Zhang, J. Yu, Adv. Mater., 2019, 31, e1902868.
[20]	D. T. Genna, A. G. Wong-Foy, A. J. Matzger, M. S. Sanford, J. Am. Chem. Soc., 2013, 135, 10586-10589.
[21]	Q. Xie, W. He, S. Liu, C. Li, J. Zhang, P. K. Wong, Chin. J. Catal., 2020, 41, 140-153.
[22]	W. Yu, D. Xu, T. Peng, J. Mater. Chem. A, 2015, 3, 19936-19947.
[23]	D. Li, Y. Huang, S. Li, C. Wang, Y. Li, X. Zhang, Y. Liu, Chin. J. Catal., 2020, 41, 154-160.
[24]	X. Liu, M. Ye, S. Zhang, G. Huang, C. Li, J. Yu, P. K. Wong, S. Liu, J. Mater. Chem. A, 2018, 6, 24245-24255.
[25]	J. Bi, W. Fang, L. Li, J. Wang, S. Liang, Y. He, M. Liu, L. Wu, Macromol. Rapid Commun., 2015, 36, 1799-1805.
[26]	M. Liu, Q. Huang, S. Wang, Z. Li, B. Li, S. Jin, B. Tan, Angew. Chem. Int. Ed., 2018, 57, 11968-11972.
[27]	S. Kuecken, A. Acharjya, L. Zhi, M. Schwarze, R. Schomacker, A. Thomas, Chem. Commun., 2017, 53, 5854-5857.
[28]	Z. A. Lan, Y. Fang, Y. Zhang, X. Wang, Angew. Chem., Int. Ed., 2018, 57, 470-474.
[29]	K. Cui, W. Zhong, L. Li, Z. Zhuang, L. Li, J. Bi, Y. Yu, Small, 2019, 15, 1804419.
[30]	W. Huang, B. C. Ma, H. Lu, R. Li, L. Wang, K. Landfester, K. A. I. Zhang, ACS Catal., 2017, 7, 5438-5442.
[31]	H. S. Jena, C. Krishnaraj, G. Wang, K. Leus, J. Schmidt, N. Chaoui, P. Van Der Voort, Chem. Mater., 2018, 30, 4102-4111.
[32]	S. Padmanaban, G. H. Gunasekar, M. Lee, S. Yoon, ACS Sustain. Chem. Eng., 2019, 7, 8893-8899.
[33]	Y. Ren, D. Zeng, W. J. Ong, Chin. J. Catal., 2019, 40, 289-319.
[34]	H. Zhong, Z. Hong, C. Yang, L. Li, Y. Xu, X. Wang, R. Wang, ChemSusChem, 2019, 12, 4493-4499.
[35]	S. Hug, M. E. Tauchert, S. Li, U. E. Pachmayr, B. V. Lotsch, J. Mater. Chem., 2012, 22, 13956-13964.
[36]	H. Zhong, C. Yang, L. Li, Y. Xu, X. Wang, R. Wang, ChemSusChem, 2019, 12, 4493-4499.
[37]	Q. Wang, W. Wang, L. Zhang, Y. Su, K. Wang, H. Wu, J. Mater. Sci. Technol., 2018, 34, 2337-2341.
[38]	M. Liu, Q. Huang, S. Wang, Z. Li, B. Li, S. Jin, B. Tan, Angew. Chem. Int. Ed., 2018, 57, 11968-11972.
[39]	Z. Zhou, W. Zhong, K. Cui, Z. Zhuang, L. Li, L. Li, J. Bi, Y. Yu, Chem. Commun., 2018, 54, 9977-9980.
[40]	K. Wang, L. Yang, X. Wang, L. Guo, G. Cheng, C. Zhang, S. Jin, B. Tan, A. Cooper, Angew. Chem. Int. Ed., 2017, 56, 14149-14153.
[41]	J. Low, B. Cheng, J. Yu, Appl. Surf. Sci., 2017, 392, 658-686.
[42]	Y. Xia, Z. Tian, T. Heil, A. Meng, B. Cheng, S. Cao, J. Yu, M. Antonietti, Joule, 2019, 3, 2792-2805.
[43]	E. X. Han, Y. Y. Li, Q. H. Wang, W. Q. Huang, L. Luo, W. Hu, G. F. Huang, J. Mater. Sci. Technol., 2019, 35, 2288-2296.
[44]	J. Low, J. Yu, M. Jaroniec, S. Wageh, A. A. Al-Ghamdi, Adv. Mater., 2017, 29, 1601694.
[45]	Y. Xu, Y. Ye, T. Liu, X. Wang, B. Zhang, M. Wang, H. Han, C. Li, J. Am. Chem. Soc, 2016, 138, 10726-10729.

共价三嗪框架复合Co单活性位点光催化制合成气

Encapsulation of Co single sites in covalent triazine frameworks for photocatalytic production of syngas

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 7

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[5]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[6]	邹心仪, 顾均. 酸性条件下二氧化碳高效电还原策略[J]. 催化学报, 2023, 52(9): 14-31.
[7]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[8]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[9]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[10]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[11]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[12]	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.
[13]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[14]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.
[15]	刘德法, 孙彬, 白硕杰, 高婷婷, 周国伟. 双助催化剂Ag/Ti₃C₂/TiO₂分层花状微球用于增强光催化产氢活性[J]. 催化学报, 2023, 50(7): 273-283.