分子筛限域单位点钴体系催化芳香族化合物C-H键自调节高效氧化

doi:10.1016/S1872-2067(23)64579-6

催化学报 ›› 2024, Vol. 57: 133-142.DOI: 10.1016/S1872-2067(23)64579-6

分子筛限域单位点钴体系催化芳香族化合物C-H键自调节高效氧化

党健^a^,^b, 李玮杰^a^,^b, 秦斌^a^,^*(), 柴玉超^a, 武光军^a, 李兰冬^a^,^*()

^a南开大学化学学院, 有机新物质创造前沿科学中心, 天津 300071
^b南开大学材料科学与工程学院, 天津 300350

收稿日期:2023-10-15 接受日期:2023-12-08 出版日期:2024-02-18 发布日期:2024-02-10
通讯作者: * 电子信箱: qinbin@nankai.edu.cn (秦斌), lild@nankai.edu.cn (李兰冬).
基金资助:
国家自然科学基金(22202107);国家自然科学基金(22025203);国家自然科学基金(22121005);中央高校基本科研业务费专项资金(南开大学)

Self-adjusted reaction pathway enables efficient oxidation of aromatic C-H bonds over zeolite-encaged single-site cobalt catalyst

Jian Dang^a^,^b, Weijie Li^a^,^b, Bin Qin^a^,^*(), Yuchao Chai^a, Guangjun Wu^a, Landong Li^a^,^*()

^aFrontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China
^bSchool of Materials Science and Engineering, Nankai University, Tianjin 300350, China

Received:2023-10-15 Accepted:2023-12-08 Online:2024-02-18 Published:2024-02-10
Contact: * E-mail: qinbin@nankai.edu.cn (B. Qin), lild@nankai.edu.cn (L. Li).
Supported by:
National Natural Science Foundation of China(22202107);National Natural Science Foundation of China(22025203);National Natural Science Foundation of China(22121005);Fundamental Research Funds for the Central Universities (Nankai University)

摘要/Abstract

摘要：

通过芳香族化合物的碳-氢键活化与选择氧化, 可以将廉价芳香烃类原料转化为高附加值含氧产品, 因此, 该反应在基础研究和工业生产中均受到广泛关注. 传统的苯乙酮生产工艺存在毒性底物使用、催化剂回收困难、反应条件苛刻以及产物收率低等问题. 通过大量的研究探索, 科研人员进一步改进其生产工艺, 利用环烷酸钴作为均相催化剂, 实现了无溶剂条件下分子氧直接选择氧化乙苯生成苯乙酮. 相比均相催化, 多相催化在催化剂回收和产物分离方面具有优势, 更适合工业化生产. 因此, 开发用于乙苯选择氧化制苯乙酮的高效稳定多相催化体系非常重要, 但具有较大挑战.

本文采用原位配体保护的水热合成法将钴配合物(钴-二乙烯三胺)封装在Y型分子筛中, 并经进一步焙烧去除配体成功制得Co@Y分子筛催化剂. 在无溶剂、无添加剂的条件下, 单位点Co作为Co@Y分子筛催化剂的活性位点可催化乙苯选择氧化生成苯乙酮. X射线粉末衍射、透射电镜、紫外可见光吸收光谱和固体核磁共振谱等结果表明, 该单位点Co(Co²⁺)通过与骨架氧原子作用稳定限域在Y型分子筛中. 为明确Co@Y分子筛催化剂中单位点Co在乙苯氧化反应中所起的重要作用, 本文还对比了不同后合成方法所制备的Y分子筛(Co/Y,Co-Y)催化剂及工业环烷酸钴催化剂的催化性能. 结果表明, 在相同反应条件下, Co@Y分子筛催化剂表现出最高的催化性能, 也说明在乙苯氧化反应过程中Co@Y分子筛催化剂的单位点Co有别于上述其他催化剂的活性位点. 此外, 在Co@Y催化剂热过滤实验中未检测出Co物种浸出, 表明Co@Y分子筛催化乙苯氧化反应为多相催化过程, 并且在多次循环测试后, Co@Y催化剂结构和反应活性均未发生明显变化. 这两项实验均表明Co@Y催化剂具有高稳定性. 值得注意的是, 在乙苯氧化反应过程中观察到自加速现象, 为此进行了对比实验(添加苯甲醛或1-苯乙醇的对比实验)和反应动力学分析. 结果表明, 痕量苯甲醛或1-苯乙醇的加入会显著改变Co@Y催化剂在乙苯氧化反应中的催化行为, 痕量苯甲醛的加入可将反应表观活化能从69.7降至53.7 kJ/mol. 本文也通过第一性原理密度泛函理论(DFT)计算系统研究了Co@Y分子筛催化剂单位点Co处乙苯选择氧化反应机理及反应过程中自加速现象产生的原因. DFT计算结果结合上述对比实验和反应动力学分析结果表明, 加入痕量苯甲醛或者1-苯乙醇后部分乙苯会直接氧化生成苯乙酮, 而非通过乙苯→1-苯乙醇→苯乙酮的途径生成苯乙酮. DFT计算结果也阐明反应过程中自加速现象的产生源于单位点Co处活性氧物种(O*)的生成. 该活性氧物种在乙苯、苯甲醛和1-苯乙醇的氧化途径中均能自发生成, 并且该物种类似“引发剂”促使后续更多链式反应的发生, 在乙苯氧化反应过程中具有非常重要的作用.

综上所述, 本文为理解芳香族化合物碳-氢键选择氧化实验现象与催化作用机制提供了有益见解, 可为理性设计开发更高效的催化剂提供新思路.

关键词: 碳-氢键活化, 多相催化, Co@Y分子筛催化剂, 自加速, 活性氧物种

Abstract:

The selective oxidation of aromatic C-H bonds to high value-added oxygenated products with molecular oxygen remains a key challenge in heterogeneous catalysis. Eligible heterogeneous catalysts are pursued and the reaction mechanism is hotly debated. Herein, we report that zeolite-encaged single-site cobalt ions can efficiently catalyze the model reaction of ethylbenzene aerobic oxidation to acetophenone, outperforming the industrial benchmark catalyst cobalt naphthenate under identical conditions. The self-accelerating phenomenon is observed in the progress of ethylbenzene aerobic oxidation, corresponding to the self-adjusted reaction pathway as revealed by kinetic studies and density functional theory calculations. The formation of reactive O* species on Co sites, resembling the well-known α-O on Fe sites, is identified to be responsible for the self-adjusted reaction pathway of aromatic C-H bond oxidation.

Key words: C-H bonds activation, Heterogeneous catalysis, Co@Y zeolite, Self-accelerating, Reactive O* species

党健, 李玮杰, 秦斌, 柴玉超, 武光军, 李兰冬. 分子筛限域单位点钴体系催化芳香族化合物C-H键自调节高效氧化[J]. 催化学报, 2024, 57: 133-142.

Jian Dang, Weijie Li, Bin Qin, Yuchao Chai, Guangjun Wu, Landong Li. Self-adjusted reaction pathway enables efficient oxidation of aromatic C-H bonds over zeolite-encaged single-site cobalt catalyst[J]. Chinese Journal of Catalysis, 2024, 57: 133-142.

×
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(23)64579-6

https://www.cjcatal.com/CN/Y2024/V57/I2/133

图/表 5

Fig. 1. Molecular structure of Co@Y and cobalt naphthenate. Co: navy; O: red; Si: yellow; Al: magenta; C: grey; H: white.

Fig. 2. Catalytic performance in EB selective oxidation. EB conversion and product distribution in EB selective oxidation over cobalt naphthenate (a) and Co@Y (b) catalysts. (c) Literature survey of heterogeneous catalysts for EB selective oxidation. Base metal catalysts are shown in circle and noble metal catalysts are shown in square [8??-11,50????????????????-67]. (d) Recycling test of Co@Y catalyst in EB selective oxidation. (one: acetophenone, ol: 1-phenylethanol, acid: benzoic acid, hyde: benzaldehyde). Reaction conditions: 65 μL cobalt naphthenate or 0.17 g Co@Y (both containing ~8.5 mg cobalt), 20 mL EB, 2 mmol biphenyl, 1.5 MPa O2, 383 K.

Fig. 3. Kinetic analyses of relevant steps in EB oxidation. Reaction rates (a) and Arrhenius plots (b) of EB oxidation to ACP over Co@Y catalyst. Reaction rates (c) and Arrhenius plots (d) of 1-phenylethanol oxidation to ACP over Co@Y catalyst. Reaction rates (e) and Arrhenius plots (f) of EB oxidation to ACP in the presence of benzaldehyde over Co@Y catalyst. Reaction conditions: 0.17 g Co@Y, 20 mL EB or 1-phenylethanol, 0 or 20 μL benzaldehyde, 2 mmol biphenyl, 1.5 MPa O2.

Fig. 4. Reaction mechanism of EB oxidation from DFT calculations. Proposed reaction pathways, optimized structures, and the corresponding energy profiles for the formation of PhCOCH3, PhCHOHCH3 and PhCHO over Co@Y zeolite at 0 K.

Fig. 5. Selective oxidation of aromatic C-H bonds. Time-dependent aromatic hydrocarbon conversion and product distribution over Co@Y catalyst. (a) Toluene; (b) propyl benzene; (c) 4-methyl-EB; (d) 1,4-diethyl benzene; (e) 4-methoxy-EB; (f) 4-nitro-EB. Reaction conditions: 0.17 g Co@Y, 20 mL substrate, 2 mmol biphenyl, 1.5 MPa O2. 423 K for toluene and 383 K for others.

参考文献

[1]	L. Ciano, G. J. Davies, W. B. Tolman, P. H. Walton, Nat. Catal., 2018, 1, 571-577.
[2]	R. Mas-Ballesté, L. Que, Science, 2006, 312, 1885-1886.
[3]	Y. J. Liu, H. Xu, W. J. Kong, M. Shang, H. X. Dai, J. Q. Yu, Nature, 2014, 515, 389-393.
[4]	M. S. Chen, M. C. White, Science, 2007, 318, 783-787.
[5]	Z. Guo, B. Liu, Q. Zhang, W. Deng, Y. Wang, Y. Yang, Chem. Soc. Rev., 2014, 43, 3480-3524.
[6]	G. Sartori, R. Maggi, Chem. Rev., 2006, 106, 1077-1104.
[7]	J. M. Seo, L. S. Tan, J. B. Baek, Adv. Mater., 2017, 29, 1606317.
[8]	C. Yi, J. Huo, Z. Liu, Chem. Eng. J., 2023, 467, 143541.
[9]	H. Wang, L. Wang, Q. Luo, J. Zhang, C. Wang, X. Ge, W. Zhang, F.-S. Xiao, Chem. Synth., 2022, 2, 2.
[10]	P. Zhang, H. Lu, Y. Zhou, L. Zhang, Z. Wu, S. Yang, H. Shi, Q. Zhu, Y. Chen, S. Dai, Nat. Commun., 2015, 6, 8446.
[11]	Y. Xiong, W. Sun, Y. Han, P. Xin, X. Zheng, W. Yan, J. Dong, J. Zhang, D. Wang, Y. Li, Nano Res., 2021, 14, 2418-2423.
[12]	W. Lv, L. Yang, B. Fan, Y. Zhao, Y. Chen, N. Lu, R. Li, Chem. Eng. J., 2015, 263, 309-316.
[13]	R. Xie, G. Fan, L. Yang, F. Li, Chem. Eng. J., 2016, 288, 169-178.
[14]	K. O. Xavier, J. Chacko, K. K. Mohammed Yusuff, Appl. Catal. A, 2004, 258, 251-259.
[15]	D. Habibi, A. R. Faraji, M. Arshadi, S. Heydari, A. Gil, Appl. Catal. A, 2013, 466, 282-292.
[16]	A. Corma, Angew. Chem. Int. Ed., 2016, 55, 6112-6113.
[17]	N. Mizuno, M. Misono, Chem. Rev., 1998, 98, 199-218.
[18]	R. Schlögl, Angew. Chem. Int. Ed., 2015, 54, 3465-3520.
[19]	M. Muzzio, Matter, 2021, 4, 3382-3384.
[20]	L. Liu, A. Corma, Chem. Rev., 2018, 118, 4981-5079.
[21]	Y. Guo, M. Wang, Q. Zhu, D. Xiao, D. Ma, Nat. Catal., 2022, 5, 766-776.
[22]	M. Taoufik, E. Le Roux, J. Thivolle-Cazat, J. M. Basset, Angew. Chem. Int. Ed., 2007, 46, 7202-7205.
[23]	A. Nandy, H. Adamji, D. W. Kastner, V. Vennelakanti, A. Nazemi, M. Liu, H. J. Kulik, ACS Catal., 2022, 12, 9281-9306.
[24]	G. Chen, Y. Zhao, G. Fu, P. N. Duchesne, L. Gu, Y. Zheng, X. Weng, M. Chen, P. Zhang, C.-W. Pao, J.-F. Lee, N. Zheng, Science, 2014, 344, 495-499.
[25]	A. Corma, H. Garcia, Chem. Rev., 2002, 102, 3837-3892.
[26]	Y. Chai, W. Dai, G. Wu, N. Guan, L. Li, Acc. Chem. Res., 2021, 54, 2894-2904.
[27]	L. Liu, A. Corma, Nat. Rev. Mater., 2021, 6, 244-263.
[28]	Q. Zhang, S. Gao, J. Yu, Chem. Rev., 2023, 123, 6039-6106.
[29]	P. Del Campo, C. Martínez, A. Corma, Chem. Soc. Rev., 2021, 50, 8511-8595.
[30]	C. Gao, F. Lyu, Y. Yin, Chem. Rev., 2021, 121, 834-881.
[31]	Y. Chai, W. Shang, W. Li, G. Wu, W. Dai, N. Guan, L. Li, Adv. Sci., 2019, 6, 1900299.
[32]	S. Goel, S. I. Zones, E. Iglesia. J. Am. Chem. Soc. 2014, 136, 15280-15290.
[33]	X. Deng, R. Bai, Y. Chai, Z. Hu, N. Guan, L. Li, CCS Chem., 2022, 4, 949-962.
[34]	W. Li, G. Wu, W. Hu, J. Dang, C. Wang, X. Weng, I. da Silva, P. Manuel, S. Yang, N. Guan, L. Li, J. Am. Chem. Soc., 2022, 144, 4260-4268.
[35]	J. Mielby, J. O. Abildstrøm, F. Wang, T. Kasama, C. Weidenthaler, S. Kegnæs, Angew. Chem. Int. Ed., 2014, 53, 12513-12516.
[36]	M. Babucci, A. Guntida, B. C. Gates, Chem. Rev., 2020, 120, 11956-11985.
[37]	H. J. Cho, D. Kim, B. Xu, ACS Catal., 2020, 10, 8850-8859.
[38]	L. Liu, M. Lopez-Haro, J. A. Perez-Omil, M. Boronat, J. J. Calvino, A. Corma, Nat. Commun. 2022, 13, 821.
[39]	Y. Chai, S. Liu, Z. J. Zhao, J. Gong, W. Dai, G. Wu, N. Guan, L. Li, ACS Catal., 2018, 8, 8578-8589.
[40]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[41]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[42]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[43]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[44]	J. Wellendorff, K. T. Lundgaard, A. Møgelhøj, V. Petzold, D. D. Landis, J. K. Nørskov, T. Bligaard, K. W. Jacobsen, Phys. Rev. B, 2012, 85, 325149.
[45]	L. Sun, Y. Wang, C. Wang, Z. Xie, N. Guan, L. Li, Chem, 2021, 7, 1557-1568.
[46]	G. Henkelman, H. Jónsson, J. Chem. Phys., 2000, 113, 9978-9985.
[47]	G. Henkelman, B. P. Uberuaga, H. Jónsson, J. Chem. Phys., 2000, 113, 9901-9904.
[48]	Q. Tang, Q. Zhang, H. Wu, Y. Wang, J. Catal., 2005, 230, 384-397.
[49]	H. Cui, Y. Zhang, Z. Qiu, L. Zhao, Y. Zhu, Appl. Catal. B, 2010, 101, 45-53.
[50]	G. Xiang, L. Zhang, C. Yi, Z. Liu, Appl. Surf. Sci., 2022, 577, 151829.
[51]	J. Liu, W. Wang, P. Jian, L. Wang, X. Yan, J. Colloid Interface Sci., 2022, 614, 102-109.
[52]	Z. Wang, Y. Jiang, Y. Li, H. Huo, T. Zhao, D. Li, K. Lin, X. Xu, Chem. Eur. J., 2019, 25, 4175-4183.
[53]	M. I. bin Saiman, G. L. Brett, R. Tiruvalam, M. M. Forde, K. Sharples, A. Thetford, R. L. Jenkins, N. Dimitratos, J. A. Lopez-Sanchez, D. M. Murphy, D. Bethell, D. J. Willock, S. H. Taylor, D. W. Knight, C. J. Kiely, G. J. Hutchings, Angew. Chem. Int. Ed., 2012, 51, 5981-5985.
[54]	L. Kalita, L. Saikia, ChemistrySelect, 2020, 5, 4848-4855.
[55]	A. Peng, M. C. Kung, R. R. O. Brydon, M. O. Ross, L. Qian, L. J. Broadbelt, H. H. Kung, Sci. Adv., 2020, 6, eaax6637.
[56]	Y. Liu, Y. Zheng, D. Feng, L. Zhang, L. Zhang, X. Song, Z. A. Qiao, Angew. Chem. Int. Ed., 2023, 62, e202306261.
[57]	J. L. K. Gbe, K. Ravi, E. K. Tillous, A. Arya, M. Grafouté, A. V. Biradar, ACS Appl. Mater. Interfaces, 2023, 15, 17879-17892.
[58]	W. F. Xu, W. J. Chen, D. C. Li, B. H. Cheng, H. Jiang, Ind. Eng. Chem. Res., 2019, 58, 3969-3977.
[59]	M. Arshadi, M. Ghiaci, A. Rahmanian, H. Ghaziaskar, A. Gil, Appl. Catal. B, 2012, 119- 120, 81-90.
[60]	J. Ren, Y. Zhou, H. Miao, C. Wang, S. Lv, M. Song, F. Li, M. Feng, Z. Chen, Dalton Trans., 2023, 52, 6398-6406.
[61]	S. Nie, J. Wang, X. Huang, X. Niu, L. Zhu, X. Yao, ACS Appl. Nano Mater., 2018, 1, 6567-6574.
[62]	S. M. Hosseini, M. Ghiaci, S. A. Kulinich, W. Wunderlich, H. S. Ghaziaskar, A. J. Koupaei, Appl. Catal. A, 2022, 630, 118456.
[63]	J. Liu, A. Luo, L. Wang, P. Jian, X. Yan, Fuel, 2023, 332, 126117.
[64]	Z. Liu, S. Sun, F. Yang, H. Liu, Y. Sun, N. Ta, G. Zhang, S. Che, Y. Li, J. Colloid Interface Sci., 2023, 632, 237-248.
[65]	J. Liu, R. Meng, P. Jian, R. Jian, ACS Sustainable Chem. Eng., 2020, 8, 16791-16802.
[66]	S. Xu, H. Li, J. Du, J. Tang, L. Wang, ACS Sustainable Chem. Eng., 2018, 6, 6418-6424.
[67]	G. Zhang, D. Wang, P. Feng, S. Shi, C. Wang, A. Zheng, G. Lü, Z. Tian, Chin. J. Catal., 2017, 38, 1207-1215.
[68]	A. Sakthivel, P. Selvam, J. Catal., 2002, 211, 134-143.
[69]	I. Hermans, J. Peeters, P. A. Jacobs, J. Org. Chem., 2007, 72, 3057-3064.
[70]	S. U. Nandanwar, S. Rathod, V. Bansal, V. V. Bokade, Catal. Lett., 2021, 151, 2116-2131.
[71]	B. E. R. Snyder, P. Vanelderen, M. L. Bols, S. D. Hallaert, L. H. Böttger, L. Ungur, K. Pierloot, R. A. Schoonheydt, B. F. Sels, E. I. Solomon, Nature, 2016, 536, 317-321.
[72]	M. L. Bols, B. E. R. Snyder, H. M. Rhoda, P. Cnudde, G. Fayad, R. A. Schoonheydt, V. Van Speybroeck, E. I. Solomon, B. F. Sels, Nat. Catal., 2021, 4, 332-340.
[73]	M. L. Bols, J. Devos, H. M. Rhoda, D. Plessers, E. I. Solomon, R. A. Schoonheydt, B. F. Sels, M. Dusselier, J. Am. Chem. Soc., 2021, 143, 16243-16255.

分子筛限域单位点钴体系催化芳香族化合物C-H键自调节高效氧化

Self-adjusted reaction pathway enables efficient oxidation of aromatic C-H bonds over zeolite-encaged single-site cobalt catalyst

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 15

编辑推荐

Metrics

[1]	Abhishek R. Varma, Bhushan S. Shrirame, Sunil K. Maity, Deepti Agrawal, Naglis Malys, Leonardo Rios-Solis, Gopalakrishnan Kumar, Vinod Kumar. C4二醇的发酵生产及其化学催化升级为高价值化学品的研究进展[J]. 催化学报, 2023, 52(9): 99-126.
[2]	赵梦, 徐晶, 宋术岩, 张洪杰. 核壳/蛋黄壳纳米反应器用于串联催化[J]. 催化学报, 2023, 50(7): 83-108.
[3]	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.
[4]	焦龙, 江海龙. 金属有机框架材料在催化领域的研究现状与展望[J]. 催化学报, 2023, 45(2): 1-5.
[5]	聂超, 龙向东, 刘琪, 王嘉, 展飞, 赵泽伦, 李炯, 席永杰, 李福伟. 原子分散Ru-P-Ru催化剂的制备及其在多类加氢中的高效应用[J]. 催化学报, 2023, 45(2): 107-119.
[6]	孙万军, 朱佳玉, 张美玉, 孟翔宇, 陈梦雪, 冯钰, 陈新龙, 丁勇. 钴基非均相催化剂在光催化水分解、二氧化碳还原和氮还原的研究进展与展望[J]. 催化学报, 2022, 43(9): 2273-2300.
[7]	翁雪霏, 杨双莉, 丁丁, 陈明树, 万惠霖. 宽波段原位红外吸收光谱在Pd/SiO₂和Cu/SiO₂催化剂上CO氧化中的应用[J]. 催化学报, 2022, 43(8): 2001-2009.
[8]	蒋亚飞, 刘锦程, 许聪俏, 李隽, 肖海. 打破合成氨反应中线性标度关系的碗型活性位点设计: 来自LaRuSi及其同构电子化物的启示[J]. 催化学报, 2022, 43(8): 2183-2192.
[9]	王春鹏, 王哲, 毛善俊, 陈志荣, 王勇. 多相催化剂活性位点的配位环境及其对催化性能的影响[J]. 催化学报, 2022, 43(4): 928-955.
[10]	陈辉, 张博, 梁宵, 邹晓新. 轻元素调控的贵金属催化剂在能源相关领域的应用[J]. 催化学报, 2022, 43(3): 611-635.
[11]	张涛, 韩晓驰, Nhat Truong Nguyen, 杨磊, 周雪梅. 二氧化钛基光催化剂用于二氧化碳还原和太阳燃料的生产[J]. 催化学报, 2022, 43(10): 2500-2529.
[12]	S. Wageh, Ahmed A. Al-ghamdi, 刘丽君. 光催化杀菌和诱导骨组织生长[J]. 催化学报, 2021, 42(7): 1051-1053.
[13]	刘晓玲, 陈磊, 许红中, 蒋师, 周瑜, 王军. 直接合成Beta沸石封装Pt纳米粒子用于5-羟甲基糠醛合成2,5-呋喃二甲酸[J]. 催化学报, 2021, 42(6): 994-1003.
[14]	刘晓艳, 蓝国钧, 李振清, 钱丽华, 刘健, 李瑛. 用于生物质水相加氢多相负载型金属催化剂的稳定策略[J]. 催化学报, 2021, 42(5): 694-709.
[15]	戴志锋, 唐永铨, 张飞, 熊玉兵, 王赛, 孙琦, 王亮, 孟祥举, 赵雷洪, 肖丰收. 双中心多孔聚合物作为多相催化剂实现CO₂在温和条件下高效转化[J]. 催化学报, 2021, 42(4): 618-626.