可见光响应S空位ZnIn_(2)S_(4)催化剂的制备及选择性氧化HMF研究  

Preparation of Visible Light Response ZnIn_(2)S_(4)Catalyst with S Vacancy and Its Selective Oxidation of HMF

作　　者：徐俪菲 侯浩强 马春慧 李伟[1] 罗沙 刘守新[1] XU Lifei;HOU Haoqiang;MA Chunhui;LI Wei;LUO Sha;LIU Shouxin(Material Science and Engineering College,Northeast Forestry University,Key Laboratory of Bio-bassed Matrial Science&Technology,Ministry of Education,Harbin 150040,China)

机构地区：[1]东北林业大学材料科学与工程学院,生物质材料科学与技术教育部重点实验室,黑龙江哈尔滨150040

出　　处：《林产化学与工业》2024年第2期33-41,共9页Chemistry and Industry of Forest Products

基　　金：国家自然科学基金资助项目(31971601,31890773);中央高校基本科研业务费专项资金(2572021BB12)

摘　　要：以硫代乙酰胺为硫源,采用一步法原位制备了具有丰富S空位的硫化铟锌(V S-ZIS)可见光催化剂,对其光催化5-羟甲基糠醛(HMF)选择性氧化为2,5-呋喃二甲醛(DFF)过程进行了研究,并分析了V S-ZIS光催化HMF选择性氧化制备DFF的机理。采用电子顺磁共振(EPR)波谱证实S空位的存在,采用紫外-可见漫反射光谱(UV-vis DRS)、XPS考察V S-ZIS的光学性质和元素组成,利用SEM、XRD观察催化剂的表面形貌和晶相结构。研究结果表明:一步法可以成功制备ZnIn_(2)S_(4),其呈花瓣微球状,且Zn、In、S元素均匀分布,可见光波长吸收范围为420~530 nm;制备时间对ZnIn_(2)S_(4)的晶体结构没有产生明显影响,但通过控制制备时间可以调控催化剂中S空位,制备时间2~10 h制得的样品V S-ZIS-2~V S-ZIS-10中,6 h时制得的V S-ZIS-6具有丰富的S空位。80℃加热6 h制备的V S-ZIS-6在反应时间4 h、V S-ZIS-6/HMF质量比值3.2、HMF浓度1.0 mmol/L、空气流量20 mL/min条件下选择性氧化HMF的性能最佳,HMF转化率为95.4%,DFF产率为61.8%。V S-ZIS表面丰富的S空位能够促进O 2在催化剂表面吸附活化,通过捕获光生电子生成更多O_(2)^(-)·,从而提高催化剂对HMF的选择性氧化能力。A visible light response catalyst with abundant S vacancies,zinc indium sulfide(V S-ZIS),was prepared in situ by one-step method using thioacetamide as the sulfur source.The process of selective photocatalytic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF)over V S-ZIS was studied,and the mechanism of V S-ZIS photocatalytic selective oxidation of HMF to DFF was analyzed.The existence of S vacancies was confirmed by electron paramagnetic resonance(EPR).The optical properties and elemental composition of V S-ZIS were investigated by UV-vis diffuse reflectance spectroscopy(DRS)and XPS,and the surface morphology and crystal structure of the catalyst were observed using SEM and XRD.The results showed that ZnIn_(2)S_(4)could be successfully synthesized by the one-step method.The catalyst exhibited a petal-like microsphere morphology,and the elements of Zn,In,and S were uniformly distributed.The visible light absorption range of the catalyst was 420-530 nm.The synthesis time did not has significantly effect on the crystal structure of ZnIn_(2)S_(4),while the S vacancies in the catalyst could be controlled by adjusting the synthesis time.Among the samples of V S-ZIS-2 to V S-ZIS-10 prepared at 2-10 h,the sample V S-ZIS-6 obtained at 6 h had abundant S vacancies.The V S-ZIS-6 prepared by heating at 80℃for 6 h showed the best performance for the selective oxidation of HMF under the conditions of a reaction time of 4 h,V S-ZIS-6/HMF mass ratio of 3.2,HMF concentration of 1.0 mmol/L,and air flow rate of 20 mL/min.The HMF conversion rate reached 95.4%,and the DFF yield was 61.8%.The abundant S vacancies on the surface of V S-ZIS could promote the adsorption and activation of O 2 on the catalyst surface,capturing photoinduced electrons to generate more O_(2)^(-)·,thereby enhancing the selective oxidation ability of the catalyst towards HMF.

关 键 词：硫空位 硫化铟锌 5-羟甲基糠醛 光催化 选择性氧化 2 5-呋喃二甲醛 

分 类 号：TQ35[化学工程]