Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces

Li, Fengwang; Li, Yuguang C.; Wang, Ziyun; Li, Jun; Nam, Dae‐Hyun; Lum, Yanwei; Luo, Mingchuan; Wang, Xue; Ozden, Adnan; Hung, Sung‐Fu; Chen, Bin; Wang, Yuhang; Wicks, Joshua; Xu, Yi; Li, Yilin; Gabardo, Christine M.; Dinh, Cao-Thang; Wang, Ying; Zhuang, Tao; Sinton, David; Sargent, Edward H.

doi:10.1038/s41929-019-0383-7

Cited by 510 publications

(507 citation statements)

References 52 publications

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“…Operating at a potential window of −0.45~−0.72 V vs. RHE, we found the CuPd 0.007 catalyst delivered a peak FE alcohol of 40%, accompanied by an alcohol partial current density of 277 mA cm −2 (at −0.62 V vs. RHE). This performance represents a 2-fold enhancement of alcohol current density compared to all prior CO/CO 2 R works at operating current densities >100 mA cm −2 (Supplementary Table 8) 15,17,[31][32][33][34][35] . In contrast, the bare-Cu control showed a peak FE alcohol of 27% at −0.66 V vs. RHE, in close agreement with a recent COR report using oxide-derived Cu catalysts 17 .…”

Section: Resultsmentioning

confidence: 84%

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

et al. 2020

Nat Commun

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107

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Multi-carbon alcohols such as ethanol are valued as fuels in view of their high energy density and ready transport. Unfortunately, the selectivity toward alcohols in CO 2 /CO electroreduction is diminished by ethylene production, especially when operating at high current densities (>100 mA cm −2). Here we report a metal doping approach to tune the adsorption of hydrogen at the copper surface and thereby promote alcohol production. Using density functional theory calculations, we screen a suite of transition metal dopants and find that incorporating Pd in Cu moderates hydrogen adsorption and assists the hydrogenation of C 2 intermediates, providing a means to favour alcohol production and suppress ethylene. We synthesize a Pd-doped Cu catalyst that achieves a Faradaic efficiency of 40% toward alcohols and a partial current density of 277 mA cm −2 from CO electroreduction. The activity exceeds that of prior reports by a factor of 2.

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Section: Resultsmentioning

confidence: 84%

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

et al. 2020

Nat Commun

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107

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“…[20][21][22][23] To improve the selectivity of C2 + alcohols, different methods have been applied to modify the Cu-based catalysts, including modifying morphology, [24] using two metals, [25] doping with a heteroatom, [26] and modifying with other molecules. [27] These methods mainly increase the production of the key C1 intermediate (CO) by another component to further enhance the production of alcohols, because the selectivity of C2 + products can be tuned by the coverage of CO. [28] Despite these impressive efforts, the Faradaic efficiency (FE) of C2 + alcohols remains below 43 % at commercial current density (! 100 mA cm À2 ).…”

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confidence: 99%

Highly Efficient Electroreduction of CO₂ to C2+ Alcohols on Heterogeneous Dual Active Sites

et al. 2020

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Electroreduction of CO2 to liquid fuels such as ethanol and n‐propanol, powered by renewable electricity, offers a promising strategy for controlling the global carbon balance and addressing the need for the storage of intermittent renewable energy. In this work, we discovered that the composite composed of nitrogen‐doped graphene quantum dots (NGQ) on CuO‐derived Cu nanorods (NGQ/Cu‐nr) was an outstanding electrocatalyst for the reduction of CO2 to ethanol and n‐propanol. The Faradaic efficiency (FE) of C2+ alcohols could reach 52.4 % with a total current density of 282.1 mA cm−2. This is the highest FE for C2+ alcohols with a commercial current density to date. Control experiments and DFT studies show that the NGQ/Cu‐nr could provide dual catalytic active sites and could stabilize the CH2CHO intermediate to enhance the FE of alcohols significantly through further carbon protonation. The NGQ and Cu‐nr had excellent synergistic effects for accelerating the reduction of CO2 to alcohols.

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“…Among these strategies, CO 2 electroreduction, which operates under ambient pressure at room temperature, serves as one of the promising ways to promote CO 2 utilization and global carbon recycling [17][18][19][20][21] . During the process of CO 2 electroreduction, a variety of carbonaceous products, including carbon monoxide (CO), formate (HCOO -), methane (CH 4 ), ethylene (C 2 H 4 ), propylene (C 3 H 6 ), ethanol (C 2 H 5 OH), and acetate (CH 3 COO -) have been reported [22][23][24] . Especially, multi-carbon (C 2+ ) products have been widely used as key feedstocks for industrial manufacture and liquid fuels due to their unique chemical functional groups and high energy density 25 .…”

Section: Introductionmentioning

confidence: 99%

Revealing the Reaction Mechanism of C-C Coupling on Cu-based Tandem Catalysts towards CO2 Reduction

Kong¹,

Ke²,

Zhou³

et al. 2020

Preprint

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Cu-based tandem catalysts have widely been exploited to improve the catalytic performance for multi-carbon (C2+) products towards CO2 electroreduction. Nevertheless, the underlying reaction mechanism for tandem catalytic system remains ambiguity. Herein, we unraveled the relationship between the behavior of adsorbed CO intermediate (*CO) and the process of C-C coupling. Due to the low coverage of *CO, the process of C-C coupling has always been restricted for Cu catalysts. Through regulating the molar ratios of CO2 to CO in co-feeding gases, we found that the moderate surface coverage of *CO was beneficial for the electroreduction of CO2 into ethylene (C2H4). Meanwhile, the cross-coupling process between CO2 and CO was proved to be responsible for the enhanced activity of C2H4 according to isotopic labeling experiments. We constructed a tandem model with cobalt phthalocyanine (CoPc) as CO-generating component on Cu to further verify the tandem mechanism. With the introduction of CoPc onto the surface of Cu, the partial current density for C2H4 reached as high as 313 mA cm-2 at applied current density of 480 mA cm-2, which was one-fold higher than that (165 mA cm-2) of Cu film. In-situ Raman measurements further revealed that CO generated by CoPc increased the coverage of *CO on the surface of Cu, facilitating the process of C-C coupling.

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Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces

Cited by 510 publications

References 52 publications

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

Highly Efficient Electroreduction of CO₂ to C2+ Alcohols on Heterogeneous Dual Active Sites

Revealing the Reaction Mechanism of C-C Coupling on Cu-based Tandem Catalysts towards CO2 Reduction

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Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces

Cited by 510 publications

References 52 publications

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

Highly Efficient Electroreduction of CO2 to C2+ Alcohols on Heterogeneous Dual Active Sites

Revealing the Reaction Mechanism of C-C Coupling on Cu-based Tandem Catalysts towards CO2 Reduction

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Highly Efficient Electroreduction of CO₂ to C2+ Alcohols on Heterogeneous Dual Active Sites