银掺杂氮化碳负载Pd催化剂的制备及在甲酸脱氢中的应用  

Preparation of Pd-based catalyst supported on silver-doped carbon nitride and its catalytic activity in formic acid dehydrogenation

作　　者：王雨生 夏媛玉 裴瑜洁 解品红 李芳[1] 李其明[1] WANG Yusheng;XIA Yuanyu;PEI Yujie;XIE Pinhong;LI Fang;LI Qiming(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,Liaoning,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001

出　　处：《精细化工》2023年第1期117-123,共7页Fine Chemicals

基　　金：国家自然科学基金项目(21703091,21201096);辽宁省教育厅资助项目(LJKM20220724,L2019009);辽宁科技厅计划指导项目(2019-ZD-0058)。

摘　　要：以高温煅烧硝酸银预修饰的三聚氰胺为前驱体得到银掺杂氮化碳(Ag_(x)C_(3)N_(4),x为硝酸银质量占三聚氰胺质量的百分数,下同)载体,并采用浸渍还原法制备了Ag_(x)C_(3)N_(4)负载Pd催化剂(Ag_(x)C_(3)N_(4)-Pd),考察其对甲酸制氢反应的催化活性。采用XRD、TEM、EDS和XPS对载体及催化剂的活性组分进行了表征与测定。结果表明,高温煅烧硝酸银预修饰的三聚氰胺前驱体可以实现银物种直接掺杂入氮化碳体相,银的引入改变了氮化碳载体的晶相结构和微观形貌。Ag_(x)C_(3)N_(4)-Pd在甲酸分解制氢中展现了良好的催化活性,Ag_(3%)C_(3)N_(4)-Pd在323 K甲酸分解转换频率(TOF值)可达991 h^(-1),明显高于未经银掺杂氮化碳负载的C_(3)N_(4)-Pd-Ag_(3%)(656 h^(-1))。同时,Ag_(3%)C_(3)N_(4)-Pd在5次循环操作中催化活性没有出现明显下降,其在甲酸制氢中具有良好的实用性。Highly active Pd-based catalysts supported by silver-doped carbon nitride(Ag_(x)C_(3)N_(4),x is the mass ratio of silver nitrate to melamine,the same below)(Ag_(x)C_(3)N_(4)-Pd)were synthesized via impregnation reduction method with Ag_(x)C_(3)N_(4)as substrate,which was prepared by high temperature calcination of silver nitrate pre-modified melamine precursors,and then evaluated on their catalytic activity for hydrogen production of formic acid decomposition.The carriers and the active components of catalyst were characterized by XRD,TEM,EDS and XPS.The results showed that Ag was successfully doped into the bulk of C_(3)N_(4)with the crystallographic structure and microstructure of C_(3)N_(4)modified.Ag_(x)C_(3)N_(4)-Pd exhibited good catalytic activity in formic acid decomposition for hydrogen generation.The turnover frequency(TOF value)of the optimized Ag_(3%)C_(3)N_(4)-Pd catalyst could reach up to 991 h–1at 323 K,significantly higher than that of C_(3)N_(4)-Pd-Ag_(3%)(656 h–1)without Ag doping.Meanwhile,Ag_(3%)C_(3)N_(4)-Pd did not show obvious decrease in catalytic activity after recycled five times,indicating good practicability in hydrogen production from formic acid.

关 键 词：氮化碳 甲酸 银掺杂 催化剂 制氢 催化技术 

分 类 号：TQ116.2[化学工程—无机化工] O643.36[理学—物理化学]