基于希瓦氏菌基因工程菌制备集成催化剂及光催化性能

doi:10.16085/j.issn.1000-6613.2023-0019

摘要/Abstract

摘要：

以希瓦氏菌基因工程菌（Shewanella oneidensis，SO）为生物模板载体，基于其过表达半胱氨酸脱硫酶的特性，利用外源添加半胱氨酸和镉离子在细菌表面合成并固定硫化镉纳米颗粒，再进一步负载氧化锌纳米颗粒，构建三元集成光催化剂（SO/CdS/ZnO）。采用SEM、TEM、EDX、XRD和XPS等技术对集成催化剂的理化性质进行充分表征；通过光催化降解染料实验评价其光催化性能。研究结果表明，CdS和ZnO纳米颗粒能够均匀负载在生物菌体外表面。所制备的集成催化剂能够有效光降解有机染料，并且锌源添加量对催化剂的降解效率有显著影响。当醋酸锌的添加量为0.22g时，集成催化剂的光降解效率最佳，有机染料在60min内光降解效率可达约100%。此外，集成催化剂重复使用5次后，光降解有机染料的效率仍能维持在80%左右。在有机染料降解过程中CdS纳米颗粒作为光吸收剂产生光生电子和空穴，而ZnO纳米颗粒抑制了光生电子和空穴对复合，双组分的协同作用提高了光降解效率。本文为构建多组分的集成光催化剂提供了简易可行的技术路线，证明了以基因工程菌为平台材料组装半导体纳米颗粒在光催化领域具有应用前景。

关键词: 生物模板, 硫化镉, 氧化锌, 集成催化剂, 基因工程菌

Abstract:

The genetic engineering Shewanella oneidensis (SO) strain was used as a biological template, to synthesize ternary SO/CdS/ZnO integrated photocatalysts, wherein, the recombinant SO strain could overexpress cysteine desulfurase for the extracellular growth of CdS nanoparticles by adding L-cysteine and cadmium ions, and zinc oxide nanoparticles were further loaded. The physicochemical properties of SO/CdS/ZnO photocatalysts were characterized by SEM, TEM, EDX, XRD, and XPS. The catalytic performance was evaluated in the photocatalytic degradation of organic dyes. The results showed that CdS and ZnO nanoparticles were uniformly loaded on the external surface of the recombinant SO strain. The as-prepared integrated nanocatalysts could effectively photodegrade organic dyes, and the amount of zinc source showed a significant effect on the degradation efficiency. When the amount of zinc acetate was 0.22g, the best photodegradation performance was achieved, e.g., the photodegradation efficiency of organic dyes could reach 100% within 60min. Moreover, the ternary integrated nanocatalysts could be reused 5 times with more than 80% of the original photodegradation efficiency. It was found that CdS nanoparticles could produce photogenerated electrons and holes under light irradiation, while ZnO nanoparticles inhibited the recombination of e^- and h⁺, and their synergistic effect improved the photodegradation efficiency. Accordingly, we provide a simple and feasible synthetic route for the multicomponent photocatalysts, and particularly we demonstrate that the assembly of semiconductor nanoparticles on the genetic engineering microorganisms as a platform has promising prospects in photocatalysis.

Key words: biotemplate, cadmium sulphide, zinc oxide, integrated catalyst, genetic engineering bacteria

中图分类号:

TQ 018

刘亚, 李静茹, 蔡东仁, 周树锋, 王远鹏, 詹国武, 李清彪. 基于希瓦氏菌基因工程菌制备集成催化剂及光催化性能[J]. 化工进展, 2023, 42(11): 5908-5919.

LIU Ya, LI Jingru, CAI Dongren, ZHOU Shufeng, WANG Yuanpeng, ZHAN Guowu, LI Qingbiao. Preparation and photocatalysis application of integrated nanocatalysts based on genetic engineering Shewanella oneidensis strain[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5908-5919.

图/表 12

图1 原始希瓦氏菌的SEM图(a)和TEM图(c)；SO/CdS复合物的SEM图(b)、TEM图(d)和EDX元素分布图(e)

图2 不同样品的XRD谱图

图3 SO/CdS/ZnO(0.22)样品的高分辨率XPS光谱图

图4 SO、SO/CdS、SO/CdS/ZnO(0.22)样品的二维和三维AFM图像

图5 不同样品的氮气吸脱附等温线（插图为根据脱附数据利用BJH模型确定的孔径分布）

图6 SO/CdS/ZnO(0.22)的SEM、TEM和EDX元素图

图7 不同催化剂样品降解刚果红的性能比较（50mg/L）(a)；不同催化剂样品的降解染料反应动力学数据(b)；SO/CdS/ZnO(0.22)在不同照射时间下底物溶液的紫外可见吸收光谱图(c)；SO/CdS/ZnO(0.22)的循环使用性能(d)（图中数据均采用365nm LED光源）

表1 不同纳米复合光催化剂对染料降解反应的活性比较

光催化剂	合成方法	染料种类（浓度）	光催化剂使用量/mg	染料去除率/%	反应速率常数k/min^-1	去除时间/h	参考文献
SO/CdS/ZnO	生物模板法	刚果红（50mg/L）	10	90	0.03	1	本文
CdS/ZrO₂	化学共沉淀法	刚果红（30mg/L）	10	84	—	2	[26]
CdS/GA	化学沉淀法	刚果红（40mg/L）	40	100	0.027	2	[27]
CdS/ZnO	水热沉淀法	罗丹明B（10mg/L）	100	98	0.076	1.5	[28]
CS/CdS	模拟生物矿化	刚果红（20mg/L）	—	86	0.011	3	[29]
CdS/Cu(OH)₂/CuO@PVA	化学合成法	刚果红（10mg/L）	10	92	—	2	[30]
Co₃O₄/TiO₂/GO	溶胶-凝胶法和水热法合	刚果红（10mg/L）	50	91	—	1.5	[31]
TiO₂/ZrO₂	微波水热法	罗丹明B（10mg/L）	50	91	—	4.5	[32]
Ag/ZnO	辅助电化学沉积法	刚果红（5mg/L）	—	92	0.021	2	[33]

图8 不同催化剂添加量下刚果红的降解曲线(a)；不同SO/CdS/ZnO添加量下刚果红降解反应动力学分析(b)（图中数据均采用365nm LED光源）

图9 不同初始刚果红浓度下光催化降解曲线(a)；不同初始刚果红浓度下SO/CdS/ZnO的降解动力学分析(b)（图中数据均采用365nm LED光源）

图10 不同光源辐射下光催化降解染料对比(a)；不同光源辐射下SO/CdS/ZnO降解染料的反应动力学分析(b)（采用定制化LED光源，其中白光为Vlight灯盘模拟太阳光谱）

图11 不同样品的荧光发射光谱(a)；紫外光下的照片(b) ；在1.0V/RHE下的瞬态光电流响应(c)

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