载铜介孔碳的制备及其对H_2O_2氧化苯制苯酚的催化性能
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摘要
以羟丙基-β-环糊精为结构导向剂,以正硅酸乙酯和硝酸铜为硅源和铜源,采用不同方法制备出了系列载铜介孔碳复合材料,用氮气吸附-脱附(BET)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射分析仪(XRD)等对其进行表征分析;研究了载铜介孔碳对H_2O_2氧化苯制苯酚的催化作用,考察了铜负载量、氧化剂用量、反应温度等因素对催化反应的影响。结果表明,用软模板法制备的载铜介孔碳表现出了良好的催化性能,苯转化率为74%,苯酚选择性达98%。催化剂循环使用4次后,依然具有明显的催化效果。
A series of copper-supported mesoporous carbons were prepared with hydroxypropyl-β-cyclodextrin,tetraethoxysilane and copper nitrate through using different synthetic routes,and characterized by means of N_2 adsorption-desorption(BET),scanning electron microscopy(SEM),transmission electron microscopy(TEM)and powder X-ray diffraction(XRD).Their catalytic performance in hydroxylation of benzene with H_2 O_2 and the effects of the reaction conditions,such as copper content,temperature and oxidant content on the catalytic performance were investigated.The results showed that soft-template method had high catalytic activity.Under the optimal reaction conditions,the conversion of benzene was 74%and the selectivity of phenol was 98%.High catalytic activity was kept after reuse for 4 times.
A series of copper-supported mesoporous carbons were prepared with hydroxypropyl-β-cyclodextrin,tetraethoxysilane and copper nitrate through using different synthetic routes,and characterized by means of N_2 adsorption-desorption(BET),scanning electron microscopy(SEM),transmission electron microscopy(TEM)and powder X-ray diffraction(XRD).Their catalytic performance in hydroxylation of benzene with H_2 O_2 and the effects of the reaction conditions,such as copper content,temperature and oxidant content on the catalytic performance were investigated.The results showed that soft-template method had high catalytic activity.Under the optimal reaction conditions,the conversion of benzene was 74%and the selectivity of phenol was 98%.High catalytic activity was kept after reuse for 4 times.
引文
[1]Zhao P P,Zhang Y Y,Li D K,et al.Mesoporous polyoxometalate-based ionic hybrid as a highly effective heterogeneous catalyst for direct hydroxylation of benzene to phenol[J].Chinese Journal of Catalysis,2018,39(02):334-341.
[2]Xue B,Chen Y,Hong Y,et al.Facile synthesis of Fe-containing graphitic carbon nitride materials and their catalytic application in direct hydroxylation of benzene to phenol[J].Chinese Journal of Catalysis,2018,39(07):1263-1274.
[3]陈福山,杨涛,胡华南.VO@g-C3N4-T高效可见光催化苯羟基化制苯酚[J].精细化工,2018,35(09):1535-1541.
[4]黄思瑜,刘彤.微波辅助V/ZSM-5分子筛催化剂催化苯羟基化制备苯酚反应[J].科技通报,2017,33(12):35-38.
[5]Wang C,Hu L Y,Wang M Y,et al.Vanadium supported on graphitic carbon nitride as a heterogeneous catalyst for the direct oxidation ofbenzene to phenol[J].Chinese Journal of Catalysis,2016,37(11):2003-2008.
[6]何光裕,宋志琪,陈海群,等.一种用于苯直接羟基化制备苯酚的纳米铜─石墨烯复合催化剂及其制备方法[P].中国CN102921419A.2013-02-13.
[7]Gao X,Xu J.A new application of clay-supported vanadium oxide catalyst to selective hydroxylation of benzene to phenol[J].Appl.Clay.Sci.,2006,33(1):1-6.
[8]Xu D,Jia L H,Guo X F.Cu-doped mesoporous VOxTiO2in catalytic hydroxylation of benzene to phenol[J].Chinese Journal of Catalysis,2013,34(2):341-350.
[9]李松,黎国兰,李庆.Cu/SBA-1的合成及其对苯羟化反应的催化性能[J].化学研究与应用,2011,23(04):491-495.
[10]Makgwane P R,Ray S S.Hydroxylation of clable nanostructured CuFe mixed-oxide catalyst[J].J.Mol.Catal.A:Chem.,2015,398(3):149-157.
[11]孔岩,徐鑫杰,吴勇,等.助剂种类对Cu-MCM-41在苯羟基化反应中催化性能的影响[J].催化学报,2008,29(04):385-390.
[12]丁力浩,李雷,陈勇,等.负载型催化剂(CuO/TUD-1,CuO/MCM-41)的制备及其在一步法氧化苯合成苯酚中的应用[J].合成化学,2015,23(04):300-304.
[13]李鹏刚,王靖轩,郭飞飞,等.介孔碳的研究进展及应用[J].化工进展,2018,37(01):149-158.
[14]张宁,李育珍,夏云生,等.介孔碳材料的制备、功能化与应用研究进展[J].化学研究与应用,2018,30(07):1048-1056.
[15]林茜颉,吕荣文,曹安民.介孔碳球的制备及其催化性能研究[J].中国科学:化学,2016,46(10):1126-1130.
[16]王慧春,王发春,李宝林.基于环糊精的介孔碳材料的制备及催化性能[J].高等学校化学学报,2016,37(11):2076-2084.
[17]Wang H C,Li J T,Lin P,et al.Low temperature strategy to synthesize high surface area mesoporous hydroxypropyl-β-cyclodextrin-based silicas via benign template removal[J].Micropor.Mesopor.Mater.,2010,134(1-3):175–180.
[18]徐如人,庞文琴.分子筛与多孔材料化学[M].科学出版社,2004,649-657.
[19]徐加泉,刘慧慧,杨瑞光,等.活性炭催化苯一步羟基化制备苯酚[J].催化学报,2012,33(10):1622-1630.
[20]谢均,李桂英,胡常伟.CuO+氧化苯直接形成苯酚反应机理的理论研究[J].高等学校化学学报,2011,32(02):339-343.
[21]蒋斯扬,孔岩,吴丞,等.高Cu含量MCM-41在苯直接羟基化反应中的催化性能[J].催化学报,2006,27(5):421-426.
[22]Balducci L,Bianchi D,Bortolo R,et al.Direct oxidation of benzene to phenol with hydrogen peroxide over a modified titanium silicalite[J].Angew.Chem.,2003,115(40):5087-5090.
[23]顾晓利,何明,史以俊,等.镧改性SBA-15液相过氧化氢氧化苯制苯酚的活性考察[J].石油学报(石油加工),2010,26(03):364-370.
[24]Boricha A B,Bajaj H C,Kim T H,et al.Preparation of Highly Dispersed Pd-Cu on Silica for the Aerobic Hydroxylation of Benzene to Phenol Under Ambient Conditions[J].Catalysis Letters,2010,137(3-4):202-209.
[25]付亚红,师红丽,周广鹏,惠永海,解正峰.介孔分子筛MCM-41固载多氮杂环席夫碱与偏钒酸钠共催化氧化苯一步制备苯酚[J].应用化学,2015,32(11):1259-1267.
[2]Xue B,Chen Y,Hong Y,et al.Facile synthesis of Fe-containing graphitic carbon nitride materials and their catalytic application in direct hydroxylation of benzene to phenol[J].Chinese Journal of Catalysis,2018,39(07):1263-1274.
[3]陈福山,杨涛,胡华南.VO@g-C3N4-T高效可见光催化苯羟基化制苯酚[J].精细化工,2018,35(09):1535-1541.
[4]黄思瑜,刘彤.微波辅助V/ZSM-5分子筛催化剂催化苯羟基化制备苯酚反应[J].科技通报,2017,33(12):35-38.
[5]Wang C,Hu L Y,Wang M Y,et al.Vanadium supported on graphitic carbon nitride as a heterogeneous catalyst for the direct oxidation ofbenzene to phenol[J].Chinese Journal of Catalysis,2016,37(11):2003-2008.
[6]何光裕,宋志琪,陈海群,等.一种用于苯直接羟基化制备苯酚的纳米铜─石墨烯复合催化剂及其制备方法[P].中国CN102921419A.2013-02-13.
[7]Gao X,Xu J.A new application of clay-supported vanadium oxide catalyst to selective hydroxylation of benzene to phenol[J].Appl.Clay.Sci.,2006,33(1):1-6.
[8]Xu D,Jia L H,Guo X F.Cu-doped mesoporous VOxTiO2in catalytic hydroxylation of benzene to phenol[J].Chinese Journal of Catalysis,2013,34(2):341-350.
[9]李松,黎国兰,李庆.Cu/SBA-1的合成及其对苯羟化反应的催化性能[J].化学研究与应用,2011,23(04):491-495.
[10]Makgwane P R,Ray S S.Hydroxylation of clable nanostructured CuFe mixed-oxide catalyst[J].J.Mol.Catal.A:Chem.,2015,398(3):149-157.
[11]孔岩,徐鑫杰,吴勇,等.助剂种类对Cu-MCM-41在苯羟基化反应中催化性能的影响[J].催化学报,2008,29(04):385-390.
[12]丁力浩,李雷,陈勇,等.负载型催化剂(CuO/TUD-1,CuO/MCM-41)的制备及其在一步法氧化苯合成苯酚中的应用[J].合成化学,2015,23(04):300-304.
[13]李鹏刚,王靖轩,郭飞飞,等.介孔碳的研究进展及应用[J].化工进展,2018,37(01):149-158.
[14]张宁,李育珍,夏云生,等.介孔碳材料的制备、功能化与应用研究进展[J].化学研究与应用,2018,30(07):1048-1056.
[15]林茜颉,吕荣文,曹安民.介孔碳球的制备及其催化性能研究[J].中国科学:化学,2016,46(10):1126-1130.
[16]王慧春,王发春,李宝林.基于环糊精的介孔碳材料的制备及催化性能[J].高等学校化学学报,2016,37(11):2076-2084.
[17]Wang H C,Li J T,Lin P,et al.Low temperature strategy to synthesize high surface area mesoporous hydroxypropyl-β-cyclodextrin-based silicas via benign template removal[J].Micropor.Mesopor.Mater.,2010,134(1-3):175–180.
[18]徐如人,庞文琴.分子筛与多孔材料化学[M].科学出版社,2004,649-657.
[19]徐加泉,刘慧慧,杨瑞光,等.活性炭催化苯一步羟基化制备苯酚[J].催化学报,2012,33(10):1622-1630.
[20]谢均,李桂英,胡常伟.CuO+氧化苯直接形成苯酚反应机理的理论研究[J].高等学校化学学报,2011,32(02):339-343.
[21]蒋斯扬,孔岩,吴丞,等.高Cu含量MCM-41在苯直接羟基化反应中的催化性能[J].催化学报,2006,27(5):421-426.
[22]Balducci L,Bianchi D,Bortolo R,et al.Direct oxidation of benzene to phenol with hydrogen peroxide over a modified titanium silicalite[J].Angew.Chem.,2003,115(40):5087-5090.
[23]顾晓利,何明,史以俊,等.镧改性SBA-15液相过氧化氢氧化苯制苯酚的活性考察[J].石油学报(石油加工),2010,26(03):364-370.
[24]Boricha A B,Bajaj H C,Kim T H,et al.Preparation of Highly Dispersed Pd-Cu on Silica for the Aerobic Hydroxylation of Benzene to Phenol Under Ambient Conditions[J].Catalysis Letters,2010,137(3-4):202-209.
[25]付亚红,师红丽,周广鹏,惠永海,解正峰.介孔分子筛MCM-41固载多氮杂环席夫碱与偏钒酸钠共催化氧化苯一步制备苯酚[J].应用化学,2015,32(11):1259-1267.