Zhou Xin, Micheroni Daniel, Lin Zekai, Poon Christopher, Li Zhong, Lin Wenbin
Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
School of Chemistry and Chemical Engineering, South China University of Technology , Guangzhou, Guangdong 510640, People's Republic of China.
ACS Appl Mater Interfaces. 2016 Feb 17;8(6):4192-8. doi: 10.1021/acsami.5b11958. Epub 2016 Feb 3.
We report the synthesis of fac-M(4-amino-bipy)(CO)3X (M = Mn and X = Br or M = Re and X = Cl, with bipy = 2,2'-bipyridine), their immobilization on graphene oxide (GrO) via diazonium grafting, and the use of Re-functionalized GrO for electrocatalytic syngas production. Infrared (IR) spectroscopy, X-ray absorption fine structure (XAFS) spectroscopy, and electrocatalysis indicated successful grafting of the Re catalyst onto GrO. Re-functionalized GrO was then deposited onto a glassy carbon electrode (GCE) for CO2 reduction. Investigation of the Re-functionalized GCE for syngas production was performed in a CO2-saturated acetonitrile solution with 3.1 M H2O as the proton source and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte. Cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatography (GC) were employed to determine its CO2-to-CO conversion performance. The Re catalyst shows a turnover frequency (TOF) for generating CO up to 4.44 s(-1) with a CO/H2 ratio of 7:5.
我们报道了面式-M(4-氨基-联吡啶)(CO)3X（M = 锰且X = 溴，或M = 铼且X = 氯，其中联吡啶 = 2,2'-联吡啶）的合成，通过重氮接枝将它们固定在氧化石墨烯（GrO）上，以及使用铼功能化的GrO进行电催化合成气生产。红外（IR）光谱、X射线吸收精细结构（XAFS）光谱和电催化表明铼催化剂成功接枝到GrO上。然后将铼功能化的GrO沉积在玻碳电极（GCE）上用于二氧化碳还原。在以3.1 M水作为质子源和0.1 M六氟磷酸四丁铵（TBAPF6）作为支持电解质的二氧化碳饱和乙腈溶液中，对用于合成气生产的铼功能化GCE进行了研究。采用循环伏安法（CV）、控制电位电解（CPE）和气相色谱法（GC）来测定其二氧化碳到一氧化碳的转化性能。铼催化剂生成一氧化碳的周转频率（TOF）高达4.44 s(-1)，一氧化碳与氢气的比例为7:5。
