离子液体中Cu纳米电极上电化学还原CO_2合成碳酸二甲脂（英文）
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摘要
在不同的温度和时间下煅烧Cu片得到Cu_2O前驱体,再由Cu_2O前驱体电化学还原得到铜电极(Oxide reduced copper,OR-Cu).通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等测试手段对材料进行了表征,通过循环伏安(CV)和气质联用仪(GC-MS)等表征手段探讨了材料对CO_2的电化学催化性能以及对电合成DMC产率的影响.结果表明,OR-Cu电极的晶界以及Cu_2O初始厚度是影响材料电催化性能的主要因素.700℃下煅烧2h的Cu_2O前驱体,再经电化学还原所得到的电极具有明显的晶界及合适的Cu_2O初始厚度,具有最高的电催化活性,以其作为电极合成DMC的产率在室温下可达到87%.
New catalysts are needed to achieve lower overpotentials for desirable products during the electroreduction of CO_2.In this study,copper nanoparticles were obtained by electrochemical method.These obtained electrodes were characterized by XRD,SEM and TEM.The electrochemical properties of the obtained electrode for electrocatalytic reduction of CO_2 in the ionic liquid,1-butyl-3-methylimidazolium-tetrafluoborate(BMIMBF_4),have been evaluated by cyclic voltammogram and potentiostatic electrolysis.Results showed that,the reduction peak of CO_2 appeared at-1.7(vs.Ag)which was more positive 0.1 V than that obtained on copper electrode,meanwhile,the current density was 12 mA higher.In addition,the electrolysis experiments have been carried out under mild conditions without any toxic solvents,catalysts and supporting electrolytes,affording the dimethyl carbonate in 87% yield.
New catalysts are needed to achieve lower overpotentials for desirable products during the electroreduction of CO_2.In this study,copper nanoparticles were obtained by electrochemical method.These obtained electrodes were characterized by XRD,SEM and TEM.The electrochemical properties of the obtained electrode for electrocatalytic reduction of CO_2 in the ionic liquid,1-butyl-3-methylimidazolium-tetrafluoborate(BMIMBF_4),have been evaluated by cyclic voltammogram and potentiostatic electrolysis.Results showed that,the reduction peak of CO_2 appeared at-1.7(vs.Ag)which was more positive 0.1 V than that obtained on copper electrode,meanwhile,the current density was 12 mA higher.In addition,the electrolysis experiments have been carried out under mild conditions without any toxic solvents,catalysts and supporting electrolytes,affording the dimethyl carbonate in 87% yield.
引文
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[4]SIRIJARAENSREA J,LIMTRAKUL J.Hydrogenation of CO2to Formic Acid over a Cu-Embedded Graphene:A DFT Study[J].Appl Surf Sci,2016,364:241-248.
[5]VARELA A S,KROSCHEL M,REIER T,et al.Controlling the Selectivity of CO2 Electroreduction on Copper:The Effect of the Electrolyte Concentration and the Importance of the Local pH[J].Catal Today,2016,260:8-13.
[6]BOUAZIZI N,BARRIMOA D,NOUSIR S,et al.Montmorillonite-Supported Pd0,Fe0,Cu0and Ag0Nanoparticles:Properties and Affinity Towards CO2[J].Appl Surf Sci,2017,402:314-322.
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[8]QIN B H,WANG H J,PENG F,et al.Effect of the Surface Roughness of Copper Substrate on ThreeDimensional Tin Electrode for Electrochemical Reduction of CO2into HCOOH[J].J CO2Util,2017,21:219-223.
[9]HUANG P,CI S Q,WANG G X,et al.High-Activity Cu Nanowires Electrocatalysts for CO2Reduction[J].J CO2Util,2017,20:27-33.
[10]RACITI D,LI K J,WANG C.Highly Dense Cu Nanowires for Low-Overpotential CO2 Reduction[J].Nano Lett,2 015(10):6 829-6 835.
[11]ROBERTS F S,KUHL K P,NILSSON A.High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts[J].Angew Chem,2015,17:5 179-5 182.
[12]FENG Q J,LIU S Q,WANG X Y.Nanoporous Copper Incorporated Platinum Composites for Electrocatalytic Reduction of CO2in Ionic Liquid BMIMBF4[J].Appl Surf Sci,2012,258:5 005-5 009.
[13]LI C W,CISTON J,KANAN M W.Electroreduction of Carbon Monoxide to Liquid Fuel on OxideDerived Nanocrystalline Copper[J].Nature,2014,508:504-507.
[14]PARDALA T,MESSIASA S,SOUSAA M,et al.Syngas Production by Electrochemical CO2Reduction in an Ionic Liquid Based-Electrolyte[J].J CO2Util,2017,18:62-72.