基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

doi:10.1016/S1872-2067(21)63998-0

催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1184-1191.DOI: 10.1016/S1872-2067(21)63998-0

• 论文 • 上一篇

基于扩散强化的Pickering界面生物催化系统构建及CO₂矿化过程研究

张博禹^a, 石家福^a^,^b^,^c^,^*(), 赵阳^a, 王涵^a, 储子仪^a, 陈裕^a, 吴振华^d, 姜忠义^b^,^d^,^#()

^a天津大学环境科学与工程学院, 天津300072
^b天津化学化工协同创新中心, 天津300072
^c中国科学院过程工程研究所, 生物化学工程国家重点实验室, 北京100190
^d天津大学化工学院, 教育部绿色化工重点实验室, 天津300072

收稿日期:2021-11-09 接受日期:2021-11-09 出版日期:2022-03-05 发布日期:2022-03-01
通讯作者: 石家福,姜忠义
基金资助:
国家优秀青年科学基金项目(22122809);国家自然科学基金(21621004);天津市自然科学基金(19JCYBJC19700);生化工程国家重点实验室开放基金项目(2020KF-06)

Pickering interfacial biocatalysis with enhanced diffusion processes for CO₂ mineralization

Boyu Zhang^a, Jiafu Shi^a^,^b^,^c^,^*(), Yang Zhao^a, Han Wang^a, Ziyi Chu^a, Yu Chen^a, Zhenhua Wu^d, Zhongyi Jiang^b^,^d^,^#()

^aSchool of Environmental Science & Engineering, Tianjin University, Tianjin 300072, China
^bCollaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
^cState Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^dKey Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2021-11-09 Accepted:2021-11-09 Online:2022-03-05 Published:2022-03-01
Contact: Jiafu Shi, Zhongyi Jiang
Supported by:
National Excellent Youth Science Fund Project(22122809);National Natural Science Foundation of China(21621004);Natural Science Foundation of Tianjin(19JCYBJC19700);Open Funding Project of the State Key Laboratory of Biochemical Engineering(2020KF-06)

摘要/Abstract

摘要：

CO₂的有效利用有助于解决环境和生态问题. 碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒, 为CO₂的高效和高选择性转化提供了一种有前景的途径. 然而, 酶离开生物体后易失活, 且难以重复利用. 目前, 包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一, 但载体的存在会造成反应物CO₂内扩散阻力增加, 降低反应活性. 此外, CO₂酶促转化是一个气-液-固三相反应过程, 反应体系中CO₂的外扩散性能也需要加强.
金属有机骨架(MOFs), 特别是咪唑酯骨架(ZIFs), 常被用作酶固定化的载体. ZIFs的拓扑结构可被设计成不同形貌, 进而通过ZIFs的结构工程来加强分子向其中的内扩散. Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液. 当固体颗粒具有催化活性时, 催化剂颗粒会扩大液-液-固或气-液-固三相接触面积, 从而有效协调反应物在不同相中的扩散时间. 如果酶被用作这些颗粒的活性中心, 所制备的Pickering乳液也可能具备类似的特性, 可加强底物分子向酶的外扩散.
本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8), 原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液. ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构. ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构. 与CA@ZIF-8颗粒相比, CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布, 这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心. 利用酶活测试来研究内扩散是否通过结构工程得到了加强, 发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%, 推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离. 同时, 十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍), 从而提升了反应物浓度并显示出更高的催化活性. 本文还设计了吸附实验来进一步验证上述假设, 发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒, 说明与ZIF-8相比, 酶包埋于ZIF-L具有更强的捕获小分子的能力, 表明CO₂分子向CA@ZIF-L的扩散速度更快, 即CA@ZIF-L的十字花状结构可强化系统的内扩散过程. 进一步比较了PIBS和游离多酶体系的催化活性, 将CO₂通入每个系统, 在反应前20 min, PIBS的pH值下降速度比游离体系快得多, 说明PIBS通过在气相和液相间构建更大的界面, 缩短了CO₂向CA的扩散距离, 从而提高了催化效率, 促进了CO₂转化. 上述假设也通过扩散动力学的计算得到了验证. 为进一步研究PIBS的CO₂矿化能力, 本文开展了CaCO₃矿化反应, 发现PIBS的CaCO₃产量远高于游离多酶体系, 表明构建的PIBS在强化内外扩散方面具有显著优势. 最后, 评估了PIBS在工业应用中的性能, 由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性, 在第8个循环后, PIBS仍可保持8.9 mg/5 min的CaCO₃产量. 综上, PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.

关键词: 二氧化碳转化, 碳酸酐酶, Pickering乳液, 金属有机骨架, 扩散强化

Abstract:

Utilization of carbon dioxide (CO₂) has become a crucial and anticipated solution to address environmental and ecological issues. Enzymes such as carbonic anhydrase (CA) can efficiently convert CO₂ into various platform chemicals under ambient conditions, which offers a promising way for CO₂ utilization. Herein, we constructed a Pickering interfacial biocatalytic system (PIBS) stabilized by CA-embedded MOFs (ZIF-8 and ZIF-L) for CO₂ mineralization. Through structure engineering of MOFs and incorporation of Pickering emulsion, the internal and external diffusion processes of CO₂ during the enzymatic mineralization were greatly intensified. When CO₂ was ventilated at a flow rate of 50 mL min^-1for 1 h, the pH value of PIBS dropped from ~8.00 to ~6.50, while the average pH value of free system only dropped to ~7.15, indicating that the initial reaction rate of CO₂ mineralization of PIBS is nearly twice that of the free system. After the 8^thcycle reaction, PIBS can still produce more than 9.8 mg of CaCO₃ in 5 min, realizing efficient and continuous mineralization of CO₂.

Key words: Carbon dioxide conversion, Carbonic anhydrase, Pickering emulsion, Metal-organic frameworks, Diffusion intensification

张博禹, 石家福, 赵阳, 王涵, 储子仪, 陈裕, 吴振华, 姜忠义. 基于扩散强化的Pickering界面生物催化系统构建及CO₂矿化过程研究[J]. 催化学报, 2022, 43(4): 1184-1191.

Boyu Zhang, Jiafu Shi, Yang Zhao, Han Wang, Ziyi Chu, Yu Chen, Zhenhua Wu, Zhongyi Jiang. Pickering interfacial biocatalysis with enhanced diffusion processes for CO₂ mineralization[J]. Chinese Journal of Catalysis, 2022, 43(4): 1184-1191.

×
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)63998-0

https://www.cjcatal.com/CN/Y2022/V43/I4/1184

图/表 7

Fig. 1. Schematic preparation process of (a) CA@ZIF-L and (b) CA@ZIF-8 particles.

Fig. 2. SEM images of ZIF-L (a), CA@ZIF-L (b), ZIF-8 (c), and CA@ZIF-8 (d). FTIR spectra (e) and XRD patterns (f) of CA@ZIF-L, ZIF-L, CA@ZIF-8, and ZIF-8; SAXS data of CA@ZIF-L (g) and CA@ZIF-8 (h) with schemes showing the size of the mesopore.

Fig. 3. Bright-field images (left) and EDS elemental mapping (right) of N, Zn, and S for CA@ZIF-8 (a) and CA@ZIF-L (b).

Fig. 4. (a) Schematic diagram of CO2 conversion catalyzed by CA@ZIF-L and CA@ZIF-8 particles. (b) Degradation rate of 4-NPA by CA@ZIF-L, CA@ZIF-8, and free CA. (c) Relative activity of CA@ZIF-L and CA@ZIF-8 particles. (d) Adsorption rate of coumarin by BSA@ZIF-L and BSA@ZIF-8 particles. Notably, bovine serum albumin (BSA) that commonly applied as the substitute for expensive enzymes was adopted to prepare BSA@ZIFs particles for the adsorption experiment [44].

Fig. 5. (a) Schematic construction process of PIBS enabled by CA@ZIF-L particles. (b) Water contact angles of CA@ZIF-L, CA@ZIF-8, ZIF-L, and ZIF-8 particles. (c) Photograph and optical microscope images of Pickering emulsion stabilized by CA@ZIF-L particles.

Fig. 6. Schematic conversion of CO2 by PIBS (a) and free system (b). When CO2 was introduced at a flow rate of 50 (c) and 100 (d) mL min-1, the pH curve of the PIBS or free system constructed by CA@ZIF-L and CA@ZIF-8 particles.

Fig. 7. (a) Schematic conversion and mineralization of CO2 by CA@ZIFs PIBS. (b) CaCO3 production catalyzed by the PIBS and free systems. (c) Recyclability of CA@ZIF-L PIBS and CA@ZIF-8 PIBS.

参考文献

[1]	I. Berg, Appl. Environ. Microbiol., 2011, 77, 1925-1936.
[2]	C. Hermida, M. Kapralov, J. Galmés, Plant Physiol., 2016, 171, 2549-2561.
[3]	P. R. Yaashikaa, P. S. Kumar, S. J. Varjani, A. Saravanan, J. CO₂ Utili., 2019, 33, 131-147.
[4]	T. T. Zhao, G. H. Feng, W. Chen, Y.-F. Song, X. Dong, G.-H. Li, H.-J. Zhang, W. Wei, Chin. J. Catal., 2019, 40, 1421-1437.
[5]	K. Valegard, P. J. Andralojc, R. P. Haslam, F. G. Pearce, G. K. Eriksen, P. J. Madgwick, A. K. Kristoffersen, M. van Lun, U. Klein, H. C. Eilertsen, M. A. J. Parry, I. Andersson, J. Biol. Chem., 2018, 293, 13033-13043.
[6]	A. K. Itakura, K. X. Chan, N. Atkinson, L. Pallesen, L. Wang, G. Reeves, W. Patena, O. Caspari, R. Roth, U. Goodenough, A. J. McCormick, H. Griffiths, M. C. Jonikas, Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 18445-18454.
[7]	P. L. Cummins, B. Kannappan, J. E. Gready. Front. Plant Sci., 2018, 9, 183.
[8]	S. L. Cao, D. M. Yue, X. H. Li, T. J. Smith, N. Li, M.-H. Zong, H. Wu, Y.-Z. Ma, W.-Y. Lou, ACS Sustainable Chem. Eng., 2016. 4, 3586-3595.
[9]	S. Cao, P. Xu, Y. Ma, X. Yao, Y. Yao, M. Zong, X. Li, W. Lou, Chin. J. Catal., 2016, 37, 1814-1823.
[10]	X.-C. Wei, L. Tang, Lu, Yan-Hua. Bioresour. Bioprocess., 2017, 4, 1-7.
[11]	Khwaja Salahuddin Siddiqi, Azamal Husen, Rifaqat A. K. Rao, J. Nanobiotechnol., 2018, 16, 14-93.
[12]	X. L. Wu, X. L. Wu, Y. Y. Zhang, et al. Nat. Commun., 2019, 1, 5165.
[13]	W. Liu, N. Yang, Y. Chen, S. Lirio, C. Wu, C. Lin, H. Huang, Chem. Eur. J., 2015, 21, 115-119.
[14]	A. A. Hassabo, A. M. Mousa, H. Abdel-Gawad, M. H. Selim, R. M. Abdelhameed, J. Mater. Chem. B, 2019, 7, 3268-3278.
[15]	Q. Gao, J. Xu, X. Bu. Coord. Chem. Rev., 2019, 378, 17-31.
[16]	P. Li, S. Moon, M. A. Guelta, S. P. Harvey, J. T. Hupp, O. K. Farha, J. Am. Chem. Soc., 2016, 138, 8052-8055.
[17]	M. Hartmann, X. Kostrov. Chem. Soc. Rev., 2013, 42, 6277-6289.
[18]	X. Wu, M. Hou, J. Ge. Catal. Sci. Technol., 2015, 5, 5077-5085.
[19]	C. Doonan, R. Riccò, K. Liang, D. Bradshaw, P. Falcaro, Acc. Chem. Res., 2017, 50, 1423-1432.
[20]	J. Cui, Y. Feng, T. Lin, Z. Tan, C. Zhong, S. Jia, ACS Appl. Mater. Interfaces, 2017, 9, 10587-10594.
[21]	R. Aveyard, B. P. Binks, J. H. Clint, Adv. Colloid Interface Sci., 2003, 100-102, 503-546.
[22]	S. Fujii, A. Aichi, M. Muraoka, N. Kishimoto, K. Iwahori, Y. Nakamura, I. Yamashita, J. Colloid Interface Sci., 2009, 338, 222-228.
[23]	D. G. Ortiz, C. Pochat-Bohatier, J. Cambedouzou, M. Bechelany, P. Miele, Engineering., 2020, 6, 468-482.
[24]	W. R, Proc. Royal Soc. Med., 1903, 2, 156-164.
[25]	P. Su, J. Chem. Soc., 1907, 1, 2001-2021.
[26]	T. H. Xia, C. H. Xue, Z. H. Wei, Trends Food Sci. Technol., 2021, 107, 1-15.
[27]	J. Frelichowska, M. Bolzinger, J. Valour, H. Mouaziz, J. Pelletier, Y. Chevalier, Int. J. Pharm., 2009, 368, 7-15.
[28]	A. Sharkawy, F. M. Casimiro, M. F. Barreiro, A. E. Rodrigues, Int. J. Biolo. Macromol., 2020, 147, 150-159.
[29]	M. F. Nsib, A. Maayoufi, N. Moussa, N. Tarhouni, A. Massouri, A. Houas, Y. Chevalier, J. Photochem Photobiol. A, 2013, 251, 10-17.
[30]	M. Pera-Titus, L. Leclercq, J. M. Clacens, F. De Campo, V. Nardello-Rataj, Angew. Chem. Int. Ed., 2015, 54, 2006-2021.
[31]	B. Y. Yang, L. Leclercq, J. Clacens, V. Nardello-Rataj, Green Chem., 2017, 19, 4552-4562.
[32]	N. Fessi, M. Nsib, Y. Chevalier, C. Guillard, F. Dappozze, A. Houas, L. Palmisano, F. Parrino, Langmuir, 2020, 36, 13545-13554.
[33]	S. Thickett, N. Wood, Y. Ng, P. B. Zetterlund, Nanoscale, 2014, 6, 8590-8594.
[34]	L. Qi, Z. G. Luo, X. X. Lu. ACS Sustainable Chem. Eng., 2019, 7, 127-7139.
[35]	H. Dong, Q. J. Ding, Y. F. Jiang, X. Li, W. Han, Carbohyd. Poly., 2021, 265, 118101.
[36]	A. Abd, A. Shalan, L. Mohamed, H. A. Essawy, F. Taha, A. K. F. Dyab, Polym. Eng. Sci., 2021, 61, 234-244.
[37]	S. J. Hunter, S. P. Armes. Langmuir, 2020, 36, 15463-15484.
[38]	X. C. Yang, B. Samanta, S. S. Agasti, Y. Jeong, Z. Zhu, S. Rana, O. R. Miranda, V. M. Rotello, Angew. Chem. Int. Ed., 2011, 50, 477-481.
[39]	D. E. Resasco, Chin. J. Catal., 2014, 35, 798-806.
[40]	B. Samanta, X. C. Yang, Y. Ofir, M.-H. Park, D. Patra, S. S. Agasti, O. R. Miranda, Z.-H. Mo, V. M. Rotello, Angew. Chem. Int. Ed., 2009, 48, 5341-5344.
[41]	J. F. Shi, X. L. Wang, S. H. Zhang, L. Tang, Z. Jiang, J. Mater. Chem. B, 2016, 4, 2654-2661.
[42]	G. Beaucage, J. Appl. Cryst., 1996, 29, 134-146.
[43]	D. K. Wilkins, S. B. Grimshaw, V. Receveur, C. M. Dobson, J. A. Jones, L. J. Smith, Biochemistry, 1999, 38, 16424-16431.
[44]	E. Mylonas, D. I. Svergun, J. Appl. Cryst., 2007, 40(s1), S245-S249.
[45]	G. Kaptay, Colloids Surf. A, 2006, 282-823, 387-401.
[46]	S. H. Zhang, M. N. Du, P. J. Shao, L. Wang, J. Ye, J. Chen, J. Chen,, Environ. Sci. Technol., 2018, 52, 12708-12716.

基于扩散强化的Pickering界面生物催化系统构建及CO₂矿化过程研究

Pickering interfacial biocatalysis with enhanced diffusion processes for CO₂ mineralization

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]	危长城, 张雯娜, 杨阔, 柏秀, 徐舒涛, 李金哲, 刘中民. CO₂作为化学品原料的高效利用途径: 与烷烃耦合反应[J]. 催化学报, 2023, 47(4): 138-149.
[2]	林莉, 何潇洋, 谢顺吉, 王野. CO₂电催化转化迈向大规模化的挑战与展望[J]. 催化学报, 2023, 53(10): 1-7.
[3]	陈杨屾, 阚淼, 燕帅, 张俊波, 刘坤豪, 严雅琴, 关安翔, 吕希蒙, 钱林平, 郑耿锋. 类空气浓度的二氧化碳的高效电还原[J]. 催化学报, 2022, 43(7): 1703-1709.
[4]	赵振龙, 边辑, 赵丽娜, 吴红君, 徐帅, 孙磊, 李志君, 张紫晴, 井立强. 2D ZnMOF/BiVO₄ S型异质结的构建及其可见光催化还原CO₂性能[J]. 催化学报, 2022, 43(5): 1331-1340.
[5]	王兰, 公宁, 周洲, 张启成, 彭文朝, 李阳, 张凤宝, 范晓彬. MOF衍生的分层多孔三维N-CoP_x/Ni₂P大电流密度下加速析氢[J]. 催化学报, 2022, 43(4): 1176-1183.
[6]	王琳琳, 李欣, 郝磊端, 洪崧, Alex W. Robertson, 孙振宇. 超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯[J]. 催化学报, 2022, 43(4): 1049-1057.
[7]	黄俊敏, 陈健民, 刘望喜, 张静文, 陈俊英, 李映伟. 具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢[J]. 催化学报, 2022, 43(3): 782-792.
[8]	郑灵玲, 张龙帅, 陈颖, 田磊, 江训恒, 谌莉莎, 邢秋菊, 刘小真, 吴代赦, 邹建平. 原位配体功能化策略制备共价金属有机骨架促进其析氢反应[J]. 催化学报, 2022, 43(3): 811-819.
[9]	吕希蒙, 陈锰寰, 谢朝龙, 钱林平, 张丽娟, 郑耿锋. 固态氧化物电解池中碳一分子电化学转化为可再生燃料[J]. 催化学报, 2022, 43(1): 92-103.
[10]	赵小雪, 李金择, 李鑫, 霍鹏伟, 施伟东. 金属有机框架(MOFs)基光催化剂的设计及其在太阳能燃料生产和污染物降解领域的研究进展[J]. 催化学报, 2021, 42(6): 872-903.
[11]	肖娟, 陈军伟, 欧祖翘, 赖俊杭, 俞同文, 王毅. 基于N-掺杂碳包覆Fe₃N复合材料的高效异相电芬顿降解有机物[J]. 催化学报, 2021, 42(6): 953-962.
[12]	王伟银, 林露, 齐海峰, 曹文秀, 李志, 陈少华, 邹晓轩, 陈铁红, 唐南方, 宋卫余, 王爱琴, 罗文豪. MIL-53 (Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用[J]. 催化学报, 2021, 42(5): 824-834.
[13]	郑笑笑, 齐思慧, 曹彦宁, 沈丽娟, 区泽棠, 江莉龙. 乙酸调控MIL-53(Fe)的形貌演变及其高效选择性氧化H₂S性能[J]. 催化学报, 2021, 42(2): 279-287.
[14]	郝磊端, 夏启能, 张强, Justus Masa, 孙振宇. 提高金属有机骨架材料在二氧化碳热催化转化中的性能: 策略及前景展望[J]. 催化学报, 2021, 42(11): 1903-1920.
[15]	胡念, 李小云, 刘思明, 王朝, 何小可, 侯月新, 王宇翔, 邓兆, 陈丽华, 苏宝连. 超高稳定性的等级孔碳负载高分散铜基选择性加氢催化剂[J]. 催化学报, 2020, 41(7): 1081-1090.