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- 2018
双二苯基-1-甲基咪唑膦氯化镍的制备及其电催化还原CO2的研究
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Abstract:
摘要 以二苯基-1-甲基咪唑膦（dpim）为配体制备了一种新型的配合物催化剂Ni(dpim)2Cl2. 循环伏安研究表明，Ni(dpim)2Cl2配合物在氮气气氛下表现出两步还原的电化学行为，在-0.7 V下为两电子的不可逆还原，在-1.3 V下为单电子准可逆还原. 向电解液中通入CO2后，在-1.3 V下的还原峰变得不可逆，且其峰电流从0.48 mA·cm-2增大到0.55 mA·cm-2. 在质子源（CH3OH）存在的条件下，该还原峰电流可继续增大到0.72 mA·cm-2. 该研究结果表明，Ni(dpim)2Cl2配合物对CO2还原具有良好的电催化性能，且其电催化还原过程符合ECE机理. 在-1.3 V下恒电位电解得到的还原产物主要为CO，催化转换频率（Turnover of Frenquency, TOF）为0.17 s-1.
A new Ni(dpim)2Cl2complex using 2-(diphenylphosphino)-1-methylimidazole (dpim) as ligand was prepared and served as a catalyst for the electrochemical reduction of CO2. The electrochemical redox behavior of Ni(dpim)2Cl2 in CH3CN/TPABF4 solution under nitrogen atmosphere showed the two-electron irreversible reduction at -0.7 V and one-electron quasi-reversible reduction at -1.3 V. After bubbling CO2 into the electrolyte, the reduction peak appeared at -1.3 V became irreversible and the peak current increased from 0.48 mA·cm-2 to 0.55 mA·cm-2. Moreover, the peak current at -1.3 V could further increase to 0.72 mA·cm-2 in the presence of proton source (CH3OH). These observations indicate that the Ni(dpim)2Cl2 exhibited a good electrocatalytic performance toward CO2 reduction and the electrocatalytic reduction process followed the ECE mechanism. The reduction products obtained by the potentiostatic electrolysis (at -1.3 V) were identified to be mainly CO with the catalytic conversion frequency of 0.17 s-1
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