TY - JOUR
T1 - Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks
AU - Zhong, Haixia
AU - Ghorbani-Asl, Mahdi
AU - Ly, Khoa Hoang
AU - Zhang, Jichao
AU - Ge, Jin
AU - Wang, Mingchao
AU - Liao, Zhongquan
AU - Makarov, Denys
AU - Zschech, Ehrenfried
AU - Brunner, Eike
AU - Weidinger, Inez M.
AU - Zhang, Jian
AU - Krasheninnikov, Arkady V.
AU - Kaskel, Stefan
AU - Dong, Renhao
AU - Feng, Xinliang
PY - 2020/3/16
Y1 - 2020/3/16
N2 - Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis.
AB - Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis.
UR - http://www.scopus.com/inward/record.url?scp=85081993209&partnerID=8YFLogxK
U2 - 10.1038/s41467-020-15141-y
DO - 10.1038/s41467-020-15141-y
M3 - Article
C2 - 32179738
AN - SCOPUS:85081993209
SN - 2041-1723
VL - 11
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 1409
ER -