ZIF-67/NiO/CdS复合型光催化剂的合成及其制氢性能

全文下载： 20240517.pdf

文章编号： 1672-6987（2024）05-0032-08； DOI： 10.16351/j.1672-6987.2024.05.004

王艺霖， 刘颖， 王金铭， 李维平， 张超， 吕志果*(青岛科技大学 化工学院， 山东 青岛 266042)

摘要： 报道了一种高效光催化制氢催化剂，在ZIF-67上负载NiO得到ZIF-67/NiO，再将ZIF-67/NiO与CdS复合，最终得到ZIF-67/NiO/CdS。研究表明，ZIF-67/NiO的存在可以提高CdS对可见光的利用率，催化剂带隙由2.12 eV减小至2.01 eV。以DL-乳酸作牺牲剂对所有的样品进行了光催化制氢实验，ZIF-67/NiO/CdS的H2产生速率最高可达11 98743 μmol·（h·g）-1，约为纯CdS的47倍。光电流响应及电化学阻抗测试证明了负载适量的ZIF-67/NiO能提高复合催化剂的电子迁移率，并且减小电子迁移阻力。最后初步提出了一种可行的光催化机理，NiO导带中的电子受p-n结驱动向CdS表面转移，参与制氢过程。而CdS上的光诱导空穴向相反方向转移到达ZIF-67，参与乳酸的还原。

关键词： CdS； 光催化； NiO； ZIF-67； 氢气

中图分类号： TB 333文献标志码： A

引用格式： 王艺霖， 刘颖， 王金铭， 等. ZIF-67/NiO/CdS复合型光催化剂的合成及其制氢性能［J］. 青岛科技大学学报(自然科学版), 2024, 45（5）： 32-39.

WANG Yilin, LIU Ying, WANG Jinming, et al. Synthesis and  hydrogen production performance of ZIF-67/NiO/CdS composite photocatalyst［J］. Journal of Qingdao University of Science and Technology（Natural Science Edition), 2024， 45（5）： 32-39.

Synthesis and  Hydrogen Production Performance of

ZIF-67/NiO/CdS Composite Photocatalyst

WANG Yilin, LIU Ying, WANG Jinming, LI Weiping, ZHANG Chao， LYU Zhiguo

(College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China)

Abstract: In this paper, an efficient photocatalytic catalyst for hydrogen production was reported. ZIF-67/NiO was obtained by loading NiO on ZIF-67, and then ZIF-67/NiO was combined with CdS to obtain ZIF-67/NiO/CdS. The results show that the presence of ZIF-67/NiO can improve the utilization of visible light by CdS, and the bandgap of catalyst decreases from 212 eV to 201 eV. Using DL-lactic acid as sacrificial agent, the hydrogen production rate of ZIF-67/NiO/CdS can reach 11 98743 μmol·（h·g）-1, which is about 47 times that of pure CdS. Photocurrent response and electrochemical impedance tests proved that ZIF-67/NiO could improve the electron mobility and reduce the electron mobility resistance of the composite catalyst. Finally, a feasible photocatalytic mechanism is proposed. The electrons in CB of NiO are transferred to CdS surface driven by p-n junction and participate in hydrogen production process. However, the photoinduced holes on CdS transfer to ZIF-67 in the opposite direction and participate in the reduction of lactic acid.

Key words: CdS; photocatalytic; NiO; ZIF-67; hydrogen

收稿日期：  2023-11-25

基金项目： 国家自然科学基金项目(NSFC21978141)；山东省博士基金项目(ZR2019BB010)；中国博士后科学基金项目(2020M672015).

作者简介： 王艺霖(1997—)，女.硕士研究生.*通信联系人.

Fe改性Pt/C催化剂催化混合硝基氯苯

氨解产物加氢的研究

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文章编号： 1672-6987（2024）05-0022-10； DOI： 10.16351/j.1672-6987.2024.05.003

张健， 丁军委*， 张效磊(青岛科技大学  化工学院， 山东 青岛 266042)

摘要： 使用浸渍-还原法分别制备了3%Pd/C、3%Pt/C和3%Pt-Fe/C催化剂，通过ICP、TEM、XPS等方法对催化剂的金属含量、表面形态、电子状态进行了表征。将制备的催化剂用于以混合硝基氯苯氨解后产物邻、对硝基苯胺和间硝基氯苯为原料，催化加氢合成邻、对苯二胺和间氯苯胺反应。通过对比3种催化剂，得到3%Pt-Fe/C催化剂催化效果最好。以3%Pt-Fe/C为催化剂，考察了各因素对混合硝基氯苯氨解产物加氢反应的影响,确定了反应的最优条件:起始催化剂用量08%（以反应原料的质量分数计），m（甲醇）∶m（水）=50∶50为溶剂，温度85 ℃，压力2 MPa，搅拌转速600 r·min-1。在此条件下，反应物转化率为100%，邻、对苯二胺和间氯苯胺的总收率可以达到99%以上，催化剂可重复使用19次。对新鲜和失活的Pt-Fe/C催化剂进行BET、CO化学吸附、TEM等表征，发现失活后催化剂的比表面积大幅下降，判定催化剂孔道堵塞是导致催化剂失活的主要原因。

关键词： Pt-Fe/C； 苯二胺； 间氯苯胺； 催化加氢

中图分类号： Q 612.1文献标志码： A

引用格式： 张健， 丁军委， 张效磊. Fe改性Pt/C催化剂催化混合硝基氯苯氨解产物加氢的研究［J］. 青岛科技大学学报(自然科学版), 2024, 45（5）： 22-31.

ZHANG Jian, DING Junwei, ZHANG Xiaolei. Using Fe modified Pt/C catalyst on the catalyst hydrogenation of mixed nitrochlorobenzene ammonolysis products［J］. Journal of Qing-dao University of Science and Technology（Natural Science Edition), 2024， 45（5）： 22-31.

Using Fe Modified Pt/C Catalyst on the Catalyst Hydrogenation of

Mixed Nitrochlorobenzene Ammonolysis Products

ZHANG Jian, DING Junwei, ZHANG Xiaolei

(College of Chemical  Engineering,Qingdao University of Science and Technology, Qingdao  266042, China)

Abstract: The 3%Pd/C, 3%Pt/C and 3%Pt-Fe/C catalysts were prepared by impregnation-reduction method. The metal content, surface morphology and electronic state of the catalysts were characterized by ICP, TEM and XPS. The prepared catalyst was used to catalyze the hydrogenation of o, p-nitroaniline and m-nitrochlorobenzene from the products of mixed nitrochlorobenzene ammoniolysis to synthesize o, p-phenylenediamine and m-chloroaniline. By comparing 3%Pd/C, 3%Pt/C and 3%Pt-Fe/C catalysts, the 3%Pt-Fe/C catalyst has the best catalytic effect. Using 3% Pt-Fe/C as catalyst, the influences of various factors on the hydrogenation of mixed nitrochlorobenzene aminolysates were investigated. The optimal reaction conditions were determined as follows: the initial catalyst amount was 08% (based on the mass fraction of reactive materials), m(methanol)∶m (water) =50∶50 is solvent, the temperature is 85 ℃, the pressure is 2 MPa, and the stirring speed is 600 r·min-1. Under these conditions, the reactant conversion rate is 100%, the yield of o, p-phenylenediamine and m-chloroaniline can reach more than 99%, and the catalyst can be reused for 19 times. The fresh and deactivated Pt-Fe/C catalysts were characterized by BET, CO chemisorption and TEM. It was found that the specific surface area of the catalyst decreased significantly after deactivation, and it was determined that the blockage of catalyst pore was the main cause of catalyst deactivation.

Key words: Pt-Fe/C; phenylenediamine; m-chloroaniline; catalytic hydrogenation

收稿日期：  2023-11-23

基金项目： 山东省重点研发计划项目（2019GSF109055）.

作者简介： 张健（1998—），男，硕士研究生.*通信联系人.