Electrocatalytic Reduction of CO2 to Methanol by Iron Tetradentate Phosphine Complex Through Amidation Strategy

被引：32

作者：

Bi, Jiaojiao ^{[1
,3
]}

Ho, Pengfei ^{[1
,3
]}

Liu, Fang-Wei ^{[1
,3
]}

Kang, Peng ^{[1
,2
,3
]}

机构：

[1] Chinese Acad Sci, Tech Inst Phys & Chem, Key Lab Photochem Convers & Optoelect Mat, 29 Zhongguancun East Rd, Beijing 100190, Peoples R China

[2] Tianjin Univ, Sch Chem Engn & Technol, Tianjin 300350, Peoples R China

[3] Univ Chinese Acad Sci, 19A Yuquan Rd, Beijing 100049, Peoples R China

来源：

CHEMSUSCHEM | 2019年 / 12卷 / 10期

关键词：

amidation; carbon dioxide; electrocatalysis; iron; methanol; CARBON-DIOXIDE; ELECTROCHEMICAL REDUCTION; CATALYTIC-HYDROGENATION; HOMOGENEOUS CATALYSIS; ALKYL FORMATES; BICARBONATES; DIHYDRIDE; CAPTURE; RHODIUM; AMINE;

D O I：

10.1002/cssc.201802929

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The iron complex of tetradentate tris[2-(diphenylphosphino) ethyl]phosphine (PP3), [Fe(PP3)(MeCN)(2)](BF4)(2), was able to electrocatalytically reduce CO2 to formate with a Faradaic efficiency (FE) of approximately 97.3% in acetonitrile. Upon addition of diethylamine as a cocatalyst, electrocatalytic reduction to methanol was achieved with an FE of 68.5%, and other products were formamide and formate. A mechanistic study suggested that the [FeH(PP3)](BF4) hydride complex was the active species in the electrocatalysis. Added amine as cocatalyst could react with CO2 to form carbamate, which could then be reduced to formamide and further to methanol. By contrast, free CO2 could only be reduced to formate as the end-product.

引用

页码：2195 / 2201

页数：7

共 61 条

[1] Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol [J].

Alberico, E. ;

Nielsen, M. .

CHEMICAL COMMUNICATIONS, 2015, 51 (31) :6714-6725

[2] Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal-Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2 [J].

An, Bing ;

Zhang, Jingzheng ;

Cheng, Kang ;

Ji, Pengfei ;

Wang, Cheng ;

Lin, Wenbin .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (10) :3834-3840

[3]

[Anonymous], 2005, ANGEW CHEM

[4]

[Anonymous], 2017, ANGEW CHEM-GER EDIT, DOI [DOI 10.1002/ANGE.201609077, DOI 10.1002/ange.201609077]

[5]

[Anonymous], 2010, ANGEW CHE, DOI DOI 10.1002/ANGE.201004263

[6]

[Anonymous], 2015, ANGEW CHEM INT EDIT, DOI DOI 10.1002/ange.201500939

[7] Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion [J].

Azcarate, Iban ;

Costentin, Cyrille ;

Robert, Marc ;

Saveant, Jean-Michel .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (51) :16639-16644

[8] EVIDENCE FOR A MOLECULAR-HYDROGEN COMPLEX OF RHODIUM - SOME FACTORS AFFECTING CIS-DIHYDRIDE REVERSIBLE ETA-2-DIHYDROGEN EXCHANGE [J].

BIANCHINI, C ;

MEALLI, C ;

PERUZZINI, M ;

ZANOBINI, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (18) :5548-5549

[9] ELECTROCHEMISTRY AS A DIAGNOSTIC-TOOL TO DISCRIMINATE BETWEEN CLASSICAL M-(H)2 AND NONCLASSICAL M-(H2) STRUCTURES WITHIN A FAMILY OF DIHYDRIDE AND DIHYDROGEN METAL-COMPLEXES [J].

BIANCHINI, C ;

LASCHI, F ;

PERUZZINI, M ;

OTTAVIANI, FM ;

VACCA, A ;

ZANELLO, P .

INORGANIC CHEMISTRY, 1990, 29 (18) :3394-3402

[10] RHODIUM COMPLEXES WITH TRIPODAL POLYPHOSPHINES AS EXCELLENT PRECURSORS TO SYSTEMS FOR THE ACTIVATION OF H-H AND C-H BONDS [J].

BIANCHINI, C ;

MASI, D ;

MELI, A ;

PERUZZINI, M ;

ZANOBINI, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (19) :6411-6423

← 1 2 3 4 5 6 7 →