富含氧空位的多级0D/2D Co3O4催化剂在苯乙烯环氧化反应中的应用

doi:10.1016/S1872-2067(18)63133-X

催化学报 ›› 2018, Vol. 39 ›› Issue (12): 1942-1950.DOI: 10.1016/S1872-2067(18)63133-X

富含氧空位的多级0D/2D Co₃O₄催化剂在苯乙烯环氧化反应中的应用

刘江永, 陈婷婷, 菅盘铭, 王理霞

扬州大学化学化工学院, 江苏扬州 225002

收稿日期:2018-06-04 修回日期:2018-07-03 出版日期:2018-12-18 发布日期:2018-09-26
通讯作者: 刘江永
基金资助:
江苏省高等学校自然科学研究项目（17KJB530011）；扬州大学科技创新培育基金项目（2017CXJ015）；江苏高校优势学科建设工程资助项目（PAPD）.

Hierarchical 0D/2D Co₃O₄ hybrids rich in oxygen vacancies as catalysts towards styrene epoxidation reaction

Jiangyong Liu, Tingting Chen, Panming Jian, Lixia Wang

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu, China

Received:2018-06-04 Revised:2018-07-03 Online:2018-12-18 Published:2018-09-26
Contact: 10.1016/S1872-2067(18)63133-X
Supported by:
This work was supported by the Natural Science Foundation for High Education of Jiangsu Province (17KJB530011), the Science and Technology Innovation Foundation of Yangzhou University (2017CXJ015), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

摘要/Abstract

摘要：

碳氢化合物的催化氧化是化学工业中一个非常重要的反应.在各种氧化反应中，由于环氧化物是制药工业和精细化学品生产中的重要中间体，而使得烯烃的催化环氧化反应近年来得到了广泛关注.环氧苯乙烷（SO）作为一种重要的环氧化物，广泛用于精细化学品、表面涂料、化妆品和环氧树脂等的生产过程中.合成SO的传统方法均需使用危险化学品，产生大量有害物质，且SO选择性差.因此，从绿色化学和可持续化学的观点来看，以苯乙烯为底物，研究使用H₂O₂，O₂或有机氢过氧化物作为氧化剂来制取SO的方法具有非常重要的意义.
在苯乙烯环氧化反应所使用的各种均相催化剂中，钴离子及其配合物具有较高的活性.然而，这些均相催化剂的分离和随后的再循环过程仍然是一个巨大的挑战，严重限制了它们的进一步应用.因此，多相催化剂，包括钴基催化剂，由于易于分离和回收，且反应条件较为温和，已被应用于苯乙烯的环氧化反应中.然而，它们通常需要复杂的制备方法，并且催化活性和SO选择性待提高.因此，开发简单但具有高活性和稳定性的钴基多相催化剂并将其用于苯乙烯的环氧化反应仍然是一个有趣而富有挑战性的研究.
本文通过一种简易的液相NaBH₄还原策略制备了一种富含氧空位的多级0D/2D Co₃O₄催化剂，采用XRD，Raman，SEM，TEM，EDS，XPS和N₂吸附-脱附等手段对材料的理化性质进行了系统表征.结果显示，还原处理使得初始的二维多孔的Co₃O₄片演变为具有多级结构的0D/2D Co₃O₄材料，比表面积由20.9提升至37.0 m²/g，且表面出现了丰富的氧空位，具有更多的Co²⁺物种.将所制催化剂用于苯乙烯的环氧化反应，结果显示，在优化的反应条件下，富含氧空位的0D/2D Co₃O₄催化剂的苯乙烯转化率和SO选择性分别可达到99.3%和71.4%，且具有较好的循环使用性能，其SO收率（70.9%）较初始的2D Co₃O₄催化剂（33.2%）提高了一倍多.结果表明，0D/2D Co₃O₄催化剂在苯乙烯环氧化反应中的优异性能得益于其多级的形貌结构、表面元素价态的改变和氧空位的生成所产生的协同效应.这种简易的液相还原策略是一种非常有效的催化剂处理方法，可改变催化剂形貌结构、表面元素价态和产生缺陷位，有望应用于更多的催化反应过程中.

关键词: Co₃O₄, 还原, 氧空位, 苯乙烯, 环氧化

Abstract:

Great efforts have been devoted to the developing of simple, efficient and stable heterogeneous catalysts for the styrene epoxidation reaction (SER). Metal oxides can be of industrial importance by offering an economic and green route for selectively converting styrene into styrene oxide (SO). Herein, by treating the pristine porous 2D Co₃O₄ sheets with NaBH₄ solution, a novel hierarchical structure, i.e., 0D Co₃O₄ nanoparticles decorated on 2D porous Co₃O₄ sheets, was obtained. This simple solution reduction strategy not only realizes the morphology evolution, but also induces the modification of the valence states of metal ions and the simultaneous generation of surface oxygen vacancies. The hierarchical 0D/2D Co₃O₄ hybrids rich in oxygen vacancies (OV-Co₃O₄) exhibit a much better SER performance than the Co₃O₄ sheets (P-Co₃O₄), with the yield of SO more than doubled. The excellent catalytic performance of the OV-Co₃O₄ can be ascribed to the synergistic effects regarding the hierarchical porous structure, the modification of surface chemical composition and the creation of surface oxygen vacancies.

Key words: Co₃O₄, Reduction, Oxygen vacancies, Styrene, Epoxidation

刘江永, 陈婷婷, 菅盘铭, 王理霞. 富含氧空位的多级0D/2D Co₃O₄催化剂在苯乙烯环氧化反应中的应用[J]. 催化学报, 2018, 39(12): 1942-1950.

Jiangyong Liu, Tingting Chen, Panming Jian, Lixia Wang. Hierarchical 0D/2D Co₃O₄ hybrids rich in oxygen vacancies as catalysts towards styrene epoxidation reaction[J]. Chinese Journal of Catalysis, 2018, 39(12): 1942-1950.

×
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(18)63133-X

https://www.cjcatal.com/CN/Y2018/V39/I12/1942

参考文献

[1] S. C. Hammer, G. Kubik, E. Watkins, S. Huang, H. Minges, F. H. Arnold, Science, 2017, 358, 215-218.
[2] J. Liu, Z. Wang, P. Jian, R. Jian, J. Colloid Interface Sci., 2018, 517, 144-154.
[3] G. Zhang, D. E. Wang, P. Feng, S. Shi, C. Wang, A. Zheng, G. Lü, Z. Tian, Chin. J. Catal., 2017, 38, 1207-1215.
[4] J. Liu, T. Chen, X. Yan, Z. Wang, R. Jian, P. Jian, E. Yuan, Catal. Commun., 2018, 109, 71-75.
[5] J. Liu, Y. Zhang, X. Yan, Z. Wang, F. Wu, S. Fang, P. Jian, Can. J. Chem. Eng., 2018, http://dx.doi.org/10.1002/cjce.23116.
[6] M. Turner, V. B. Golovko, O. P. H. Vaughan, P. Abdulkin, A. Berenguer-Murcia, M. S. Tikhov, B. F. G. Johnson, R. M. Lambert, Nature, 2008, 454, 981-983.
[7] M. S. C. Chan, E. Marek, S. A. Scott, J. S. Dennis, J. Catal., 2018, 359, 1-7.
[8] Q. Zhang, Y. Guo, W. Zhan, Y. Guo, L. Wang, Y. Wang, G. Lu, Chin. J. Catal., 2017, 38, 65-72.
[9] K. Yuan, T. Song, D. Wang, Y. Zou, J. Li, X. Zhang, Z. Tang, W. Hu, Nanoscale, 2018, 10, 1591-1597.
[10] N. Li, B. Yang, M. Liu, Y. Chen, J. Zhou, Chin. J. Catal., 2017, 38, 831-843.
[11] Y. Fang, Y. Chen, X. Li, X. Zhou, J. Li, W. Tang, J. Huang, J. Jin, J. Ma, J. Mol. Catal. A, 2014, 392, 16-21.
[12] J. Liu, S. Fang, R. Jian, F. Wu, P. Jian, Powder Technol., 2018, 329, 19-24.
[13] F. Pan, B. Zhang, W. Cai, Catal. Commun., 2017, 98, 121-125.
[14] B. Li, X. Luo, J. Huang, X. Wang, Z. Liang, Chin. J. Catal., 2017, 38, 518-528.
[15] J. Liu, T. Chen, P. Jian, L. Wang, X. Yan, J. Colloid Interface Sci., 2018, 526, 295-301.
[16] J. Sebastian, K. M. Jinka, R. V. Jasra, J. Catal., 2006, 244, 208-218.
[17] G. Xu, Q. H. Xia, X. H. Lu, Q. Zhang, H. J. Zhan, J. Mol. Catal. A, 2007, 266, 180-187.
[18] D. E. Hamilton, R. S. Drago, A. Zombeck, J. Am. Chem. Soc., 1987, 109, 374-379.
[19] B. Rhodes, S. Rowling, P. Tidswell, S. Woodward, S. M. Brown, J. Mol. Catal. A, 1997, 116, 375-384.
[20] Q. Tang, Y. Wang, J. Liang, P. Wang, Q. Zhang, H. Wan, Chem. Commun., 2004, 440-441.
[21] Y. Luo, J. Lin, Microporous Mesoporous Mater., 2005, 86, 23-30.
[22] Y. Li, S. Zhao, Q. Hu, Z. Gao, Y. Liu, J. Zhang, Y. Qin, Catal. Sci. Technol., 2017, 7, 2032-2038.
[23] A. P. S. Oliveira, I. S. Gomes, A. S. B. Neto, A. C. Oliveira, J. M. Filho, G. D. Saraiva, J. M. Soares, S. Tehuacanero-Cuapa, Mol. Catal., 2017, 436, 29-42.
[24] F. Yang, S. Zhou, S. Gao, X. Liu, S. Long, Y. Kong, Microporous Mesoporous Mater., 2017, 238, 69-77.
[25] A. de Brito S. Neto, L. G. Pinheiro, J. M. Filho, A. C. Oliveira, Fuel, 2015, 150, 305-317.
[26] S. Mandal, A. SinhaMahapatra, B. Rakesh, R. Kumar, A. Panda, B. Chowdhury, Catal. Commun., 2011, 12, 734-738.
[27] A. Askarinejad, M. Bagherzadeh, A. Morsali, Appl. Surf. Sci., 2010, 256, 6678-6682.
[28] N. S. Patil, B. S. Uphade, P. Jana, S. K. Bharagava, V. R. Choudhary, J. Catal., 2004, 223, 236-239.
[29] S. B. Kumar, S. P. Mirajkar, G. C. G. Pais, P. Kumar, R. Kumar, J. Catal., 1995, 156, 163-166.
[30] Q. Tang, Q. Zhang, H. Wu, Y. Wang, J. Catal., 2005, 230, 384-397.
[31] N. Masunga, G. S. Tito, R. Meijboom, Appl. Catal. A, 2018, 552, 154-167.
[32] C. Weerakkody, S. Biswas, W. Song, J. He, N. Wasalathanthri, S. Dissanayake, D. A. Kriz, B. Dutta, S. L. Suib, Appl. Catal. B, 2018, 221, 681-690.
[33] C. Zhu, S. Fu, D. Du, Y. Lin, Chem. Eur. J., 2016, 22, 4000-4007.
[34] H. Chen, M. Yang, S. Tao, G. Chen, Appl. Catal. B, 2017, 209, 648-656.
[35] H. Sun, Y. Zhao, K. Molhave, M. Zhang, J. Zhang, Nanoscale, 2017, 9, 14431-14441.
[36] J. Liu, D. Wang, M. Wang, D. Kong, Y. Zhang, J. F. Chen, L. Dai, Chem. Eng. Technol., 2016, 39, 891-898.
[37] Y. Lou, L. Wang, Z. Zhao, Y. Zhang, Z. Zhang, G. Lu, Y. Guo, Y. Guo, Appl. Catal. B, 2014, 146, 43-49.
[38] L. Li, J. Yan, T. Wang, Z. J. Zhao, J. Zhang, J. Gong, N. Guan, Nat. Commun., 2015, 6, 5881.
[39] Z. Xiao, Y. Wang, Y. C. Huang, Z. Wei, C. L. Dong, J. Ma, S. Shen, Y. Li, S. Wang, Energy Environ. Sci., 2017, 10, 2563-2569.
[40] Z. Wang, W. Wang, L. Zhang, D. Jiang, Catal. Sci. Technol., 2016, 6, 3845-3853.
[41] J. Liu, X. Yan, L. Wang, L. Kong, P. Jian, J. Colloid Interface Sci., 2017, 497, 102-107.
[42] D. Wang, Z. Y. Wang, Q. Q. Zhan, Y. Pu, J. X. Wang, N. R. Foster, L. M. Dai, Engineering, 2017, 3, 402-408.
[43] Y. P. Zhu, T. Y. Ma, M. Jaroniec, S. Z. Qiao, Angew. Chem. Int. Ed., 2017, 56, 1324-1328.
[44] Y. Wang, T. Zhou, K. Jiang, P. Da, Z. Peng, J. Tang, B. Kong, W. B. Cai, Z. Yang, G. Zheng, Adv. Energy Mater., 2014, 4, 201400696.
[45] L. Xu, Q. Jiang, Z. Xiao, X. Li, J. Huo, S. Wang, L. Dai, Angew. Chem. Int. Ed., 2016, 55, 5277-5281.
[46] L. Li, Y. Li, S. Gao, N. Koshizaki, J. Mater. Chem., 2009, 19, 8366-8371.
[47] S. K. Pardeshi, R. Y. Pawar, J. Mol. Catal. A, 2011, 334, 35-43.
[48] J. Sun, Q. Kan, Z. Li, G. Yu, H. Liu, X. Yang, Q. Huo, J. Guan, RSC Adv., 2014, 4, 2310-2317.
[49] V. R. Choudhary, R. Jha, P. Jana, Catal. Commun., 2008, 10, 205-207.
[50] R. Hu, P. Yang, Y. Pan, Y. Li, Y. He, J. Feng, D. Li, Dalton Trans., 2017, 46, 13463-13471.
[51] J. Liu, Z. Wang, X. Yan, P. Jian, J. Colloid Interface Sci., 2017, 505, 789-795.
[52] J. Liu, C. Ran, Y. Pu, J. X. Wang, D. Wang, J. F. Chen, Can. J. Chem. Eng., 2017, 95, 1297-1304.
[53] H. Su, Z. Li, Q. Huo, J. Guan, Q. Kan, RSC Adv., 2014, 4, 9990-9996.
[54] P. Zhou, Y. Wang, C. Xie, C. Chen, H. Liu, R. Chen, J. Huo, S. Wang, Chem. Commun., 2017, 53, 11778-11781.
[55] D. Chen, C. L. Dong, Y. Zou, D. Su, Y. C. Huang, L. Tao, S. Dou, S. Shen, S. Wang, Nanoscale, 2017, 9, 11969-11975.
[56] Y. Wang, M. Qiao, Y. Li, S. Wang, Small, 2018, 14, 201800136.
[57] E. W. McFarland, H. Metiu, Chem. Rev., 2013, 113, 4391-4427.
[58] J. M. López, A. L. Gilbank, T. García, B. Solsona, S. Agouram, L. Torrente-Murciano, Appl. Catal. B, 2015, 174-175, 403-412.

富含氧空位的多级0D/2D Co₃O₄催化剂在苯乙烯环氧化反应中的应用

Hierarchical 0D/2D Co₃O₄ hybrids rich in oxygen vacancies as catalysts towards styrene epoxidation reaction

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	石靖, 郭煜华, 谢飞, 章名田, 张洪涛. 氧化还原活性配体的电子效应对钌催化水氧化反应的影响[J]. 催化学报, 2023, 52(9): 271-279.
[2]	张季, 俞爱民, 孙成华. 非金属掺杂石墨烯异核双原子催化剂氮还原特性研究[J]. 催化学报, 2023, 52(9): 263-270.
[3]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[4]	洪岩, 王琦, 阚子旺, 张禹烁, 郭晶, 李思琦, 刘松, 李斌. 电化学氮还原氨反应催化剂的最新研究进展[J]. 催化学报, 2023, 52(9): 50-78.
[5]	孙嘉辰, 陈赛, 付东龙, 王伟, 王显辉, 孙国栋, 裴春雷, 赵志坚, 巩金龙. 氧扩散与表面反应在VO_x-Ce_1‒_xZr_xO₂催化丙烷脱氢反应中的影响[J]. 催化学报, 2023, 52(9): 217-227.
[6]	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.
[7]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[8]	高晖, 张恭, 程东方, 王永涛, 赵静, 李晓芝, 杜晓伟, 赵志坚, 王拓, 张鹏, 巩金龙. 构建Cu台阶位促进电催化CO₂还原制醇类化学品的研究[J]. 催化学报, 2023, 52(9): 187-195.
[9]	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.
[10]	张雯, 宋彩彩, 王嘉蔚, 蔡舒婷, 高梦语, 冯有祥, 鲁统部. 双向主客体作用促进水溶液中选择性光催化CO₂还原与醇氧化[J]. 催化学报, 2023, 52(9): 176-186.
[11]	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.
[12]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[13]	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.
[14]	李晓娟, 祁明雨, 李婧宇, 谭昌龙, 唐紫蓉, 徐艺军. PdS修饰的ZnIn₂S₄复合材料用于可见光催化硫醇偶联制备二硫化物同时产氢[J]. 催化学报, 2023, 51(8): 55-65.
[15]	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.