摘要
在碱性甘油电氧化反应中,利用电化学傅里叶变换衰减全反射谱红外光谱法,研究了薄膜流动池中滴注硼酸镍催化剂负载量对玻碳电极性能的影响.连续操作的径向流动池包括一个位于内反射元件上方50μm的钻孔电极,可实现红外光谱分析.这是在确定条件下对电催化剂进行简便和可重复筛选的一个适合的方法,同时还提供了对复杂反应(如甘油氧化)产物选择性的检测.通过对泵送电解液进行更耗时的定量高效液相色谱分析,结果表明,衰减全反射红外光谱法可快速鉴定产物.在层流条件下,水中使用0.1 M甘油和1 M KOH,流速为5μL min^(-1)时,甘油转化率较高.转化率和选择性取决于催化剂的负载量,负载量又决定了催化剂层的厚度和粗糙度.由于在更粗糙的膜中停留时间更长有利于再吸附和C-C键断裂,因此当负载量最高达210μg cm^(-2)时,甘油转化率为73%且甲酸选择性接近80%.当最低负载量为13μg cm^(-2)时,甘油转化率达到63%,甲酸选择性降至60%,相应地,C_(2)物种(如乙醇酸盐)选择性较高,为8%.因此,只有催化剂负载量较低时才能形成几微米厚度范围内的薄膜,此时才适合进行优质催化剂的筛选.
The influence of the drop-casted nickel boride catalyst loading on glassy carbon electrodes was investigated in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in alkaline glycerol electrooxidation.The continuously operated radial flow cell consisted of a borehole electrode positioned 50μm above an internal reflection element enabling operando FTIR spectroscopy.It is identified as a suitable tool for facile and reproducible screening of electrocatalysts under well-defined conditions,additionally providing access to the selectivities in complex reaction networks such as glycerol oxidation.The fast product identification by ATR-IR spectroscopy was validated by the more time-consuming quantitative HPLC analysis of the pumped electrolyte.High degrees of glycerol conversion were achieved under the applied laminar flow conditions using 0.1 M glycerol and 1 M KOH in water and a flow rate of 5μL min^(–1).Conversion and selectivity were found to depend on the catalyst loading,which determined the catalyst layer thickness and roughness.The highest loading of 210μg cm^(–2)resulted in 73%conversion and a higher formate selectivity of almost 80%,which is ascribed to longer residence times in rougher films favoring readsorption and C–C bond scission.The lowest loading of 13μg cm^(–2)was sufficient to reach 63%conversion,a lower formate selectivity of 60%,and,correspondingly,higher selectivities of C_(2)species such as glycolate amounting to 8%.Thus,only low catalyst loadings resulting in very thin films in the fewμm thickness range are suitable for reliable catalyst screening.
作者
Steffen Cychy
Sebastian Lechler
Zijian Huang
Michael Braun
Ann Cathrin Brix
Peter Blümler
Corina Andronescu
Friederike Schmid
Wolfgang Schuhmann
Martin Muhler
Steffen Cychy;Sebastian Lechler;Zijian Huang;Michael Braun;Ann Cathrin Brix;Peter Blümler;Corina Andronescu;Friederike Schmid;Wolfgang Schuhmann;Martin Muhler(Laboratory of Industrial Chemistry,Department of Chemistry and Biochemistry,Ruhr University Bochum,Universitätsstr.150,D-44801 Bochum,Germany;Technical Chemistry III and CENIDE,Faculty of Chemistry,University of Duisburg-Essen,Universitätsstr.7,D-45141,Essen,Germany;Analytical Chemistry-Center for Electrochemical Sciences(CES),Faculty of Chemistry and Biochemistry,Ruhr University Bochum,Universitätsstr.150,D-44801 Bochum,Germany;Institute of Physics,Johannes Gutenberg-University Mainz,Staudingerweg 9,D-55128 Mainz,Germany)
