The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic acti...The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).展开更多
The film by tetraphenylporphyrin ((TPP )H2) vapor deposinon on iron was investigatedby means of XPS, SEM and visible spectroscopy. N(1s) binding energy characteristic of (TPP)H2was gained directly from the deposited s...The film by tetraphenylporphyrin ((TPP )H2) vapor deposinon on iron was investigatedby means of XPS, SEM and visible spectroscopy. N(1s) binding energy characteristic of (TPP)H2was gained directly from the deposited samples. N(1s) binding energy of the surface was greatlychanged after the deposited sample was washed with solvent. It is indicated that the deposited filmis composed of an outer-layer of physically adsorbed (TPP)H2, and an inner-layer of chemicallymodified (TPP)H2.展开更多
基金supported by NSERC DG 2016-06122 and 201606589 through Discovery Grants to HBK and X.A.Z.,respectivelyby the Canada Foundation for Innovation,Canada Research Chair,and the Ontario Research Fund。
文摘The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).
基金ACKN0WLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20443002） and the Science Foundations of Henan Province for 0utstanding Young Scientists （No.0612002600）
文摘几何学优化和单身者削尖铁 tetraphenylporphyrin 氯化物 Fe ( TPP ) Cl 和铁 tetraphenylporphyrin 氯化物( Fe ( TPP ) Cl )的精力计算，铁 pentafluorophenylporphyrin 氯化物( Fe ( TPPF <SUB>20</SUB>)Cl)被使用密度执行有 STO-3G 的功能的理论( DFT ) UB3LYP *并且6-31G*基础集合分别地。电子性质和 high-lying 的结构分子的 orbitals 详细被分析。部分纺纱在 Fe 原子上与旋转反面从 Fe 原子被转移到卟啉戒指和某电子到奇电子的结果表演从卟啉戒指被转移到 Fe 原子。- 并且类型在 Fe 原子和 porphyin 戒指原因之间结合转移。氟化作用提高电子转移和建筑群的化学稳定性。高稳定性为拥有高催化的活动的建筑群是重要的。复杂表面上的氧分子激活的催化作用机制也基于分子的 orbitals 的对称被讨论。
文摘The film by tetraphenylporphyrin ((TPP )H2) vapor deposinon on iron was investigatedby means of XPS, SEM and visible spectroscopy. N(1s) binding energy characteristic of (TPP)H2was gained directly from the deposited samples. N(1s) binding energy of the surface was greatlychanged after the deposited sample was washed with solvent. It is indicated that the deposited filmis composed of an outer-layer of physically adsorbed (TPP)H2, and an inner-layer of chemicallymodified (TPP)H2.
