Sulfur-Modulated Tin Sites Enable Highly Selective Electrochemical Reduction of CO2 to Formate

Zheng, Xiaolin; Luna, Phil De; Arquer, F. Pelayo Garcı́a de; Zhang, Bo; Becknell, Nigel; Ross, Michael B.; Li, Yifan; Banis, Mohammad Norouzi; Li, Yuzhang; Liu, Min; Voznyy, Oleksandr; Dinh, Cao-Thang; Zhuang, Tao‐Tao; Stadler, Philipp; Cui, Yi; Du, Xi‐Wen; Yang, Peidong; Sargent, Edward H.

doi:10.1016/j.joule.2017.09.014

Cited by 429 publications

(306 citation statements)

References 47 publications

(81 reference statements)

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“…It achieved the maximum formate Faradaic efficiency of ≈85% and current density of ≈14 mA cm −2 at η = 680 mV in 0.5 m NaHCO 3 . In a parallel study, Sargent and co‐workers deposited SnS x on Au nanoneedles via atomic layered deposition, then electrochemically reduced it to partially remove the sulfur species and obtained the sulfur‐modulated tin (Sn(S)) catalyst for CO 2 RR ( Figure 7 a,b) . The authors suggested that the presence of remaining sulfur atoms at the surface promoted undercoordinated sites, and favored the selective electrochemical reduction of CO 2 to formate as supported by density functional theory (DFT) calculations.…”

Section: Main Group Metal–based Electrocatalysts For Selective Co2rr mentioning

confidence: 91%

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

Han

Pan

et al. 2019

Advanced Energy Materials

472

384

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Selective CO2 reduction to formic acid or formate is the most technologically and economically viable approach to realize electrochemical CO2 valorization. Main group metal–based (Sn, Bi, In, Pb, and Sb) nanostructured materials hold great promise, but are still confronted with several challenges. Here, the current status, challenges, and future opportunities of main group metal–based nanostructured materials for electrochemical CO2 reduction to formate are reviewed. Firstly, the fundamentals of electrochemical CO2 reduction are presented, including the technoeconomic viability of different products, possible reaction pathways, standard experimental procedure, and performance figures of merit. This is then followed by detailed discussions about different types of main group metal–based electrocatalyst materials, with an emphasis on underlying material design principles for promoting the reaction activity, selectivity, and stability. Subsequently, recent efforts on flow cells and membrane electrode assembly cells are reviewed so as to promote the current density as well as mechanistic studies using in situ characterization techniques. To conclude a short perspective is offered about the future opportunities and directions of this exciting field.

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Section: Main Group Metal–based Electrocatalysts For Selective Co2rr mentioning

confidence: 91%

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

Han

Pan

et al. 2019

Advanced Energy Materials

472

384

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“…Furthermore, high-curvature structures, such as nanoneedles, promote nucleation of smaller gas bubbles 27 , and benefit from field-induced reagent concentration [28][29][30][31][32] , where high local negative electric fields concentrate positively charged cations to help stabilize CO 2 reduction intermediates 33 , enhancing CO 2 RR. However, combining high-curvature morphology with Cu + promotion to enable selective chemical conversion has yet to be explored.…”

Section: Articlesmentioning

confidence: 99%

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

et al. 2018

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As energy demand continues to increase, so too do anthropogenic carbon emissions and global temperatures. Renewable energy sources such as solar, wind and hydroelectricity displace fossil fuel carbon emissions and continue to progress to wider deployment. However, long-term (seasonal) energy storage remains a challenge that must be addressed for renewables to meet a major fraction of global energy demand 1 . Carbon dioxide electroreduction to renewable fuels and feedstocks provides an energy storage solution to the seasonal variability of renewable energy sources 2 . When coupled with carbon capture technology, the carbon dioxide reduction reaction (CO 2 RR) offers a means to close the carbon cycle.CO 2 RR electrocatalysts lower energetic barriers to CO 2 reduction by stabilizing intermediates and transition states in the multistep electrochemical reduction process 3 . Copper reduces CO 2 to a wide range of hydrocarbon products such as methane, ethylene, ethanol and propanol 4 . Unfortunately, bulk copper is not selective among various carbon products, and it also suffers Faradaic efficiency (FE) losses to the competing hydrogen evolution reaction.Among possible products, C2+ hydrocarbons are highly sought in view of their commercial value. Ethylene, for example, is a precursor to the production of polyethylene, a major plastic. Selectively producing ethylene over methane circumvents costly paraffin-olefin separation 5 . Developing catalysts that work at ambient conditions to produce C2 selectively over C1 gaseous products will increase the relevance of renewable feedstocks in the chemical sector.Oxide-derived copper is one class of catalyst that has shown enhanced CO 2 RR activity and increased selectivity towards multi-carbon products [6][7][8] . The selectivity of these catalysts is dependent on structural morphology and copper oxidation state 9-17 . Electrochemical reduction of copper oxide catalyst films can lead to grain boundaries, undercoordinated sites and roughened surfaces that are hypothesized to be catalytically active sites 8,18 . Residual oxides, proposed to play a key role in catalysis, may exist after electrochemical reduction 7 . A recent report of oxygen plasma-activated oxide-derived copper catalysts achieved an ethylene FE of 60% at − 0.9 V versus reversible hydrogen electrode (RHE) 9 , with activity attributed to the presence of Cu + species. In situ hard X-ray absorption spectroscopy (hXAS) experiments have suggested stable Cu + species exist at highly negative CO 2 RR potentials of ~− 1.0 versus RHE 9 . However, the presence of Cu + species during CO 2 RR is still the subject of debate; 7,19 and in situ tracking of the copper oxidation state with time resolution during CO 2 RR has remained elusive.Morphological effects of copper nanostructures have a significant effect on the selectivity of CO 2 RR to multi-carbon products [20][21][22][23][24] . Copper catalysts with different morphologies have been synthesized through annealing, chemical treatments on thin films, colloidal synthesis and ...

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“…For instance, Bi nanosheets catalyst that are generated from atomic‐thick Bi oxycarbonate nanosheets display a FE HCOO − of ≈100% at −0.9 V and this activity is partly attributed to the presence of Bi(101) and Bi(111) facets, which are demonstrated to lower free energy barrier for formation of *OCHO radical, facilitating CO 2 RR . Similar facet dependent DFT results with Sn, In and Bi catalysts were used as theoretical evidence to justify the catalytic activity of these catalysts for CO 2 RR . In addition, SnO 2 (110) is reported to play a positive role in dictating formate generation during CO 2 RR with a number of literatures with SnO 2 nanoparticle catalysts ascribing the importance of this facet …”

Section: Active Sites In Metal‐based Catalystsmentioning

confidence: 86%

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO₂ to Value‐Added Chemicals and Fuel

Daiyan

Saputera

Masood

et al. 2020

Advanced Energy Materials

128

104

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Renewable‐electricity‐powered electrocatalytic CO2 reduction reactions (CO2RR) have been identified as an emerging technology to address the issue of rising CO2 emissions in the atmosphere. While the CO2RR has been demonstrated to be technically feasible, further improvements in catalyst performance through active sites engineering are a prerequisite to accelerate its commercial feasibility for utilization in large CO2‐emitting industrial sources. Over the years, the improved understanding of the interaction of CO2 with the active sites has allowed superior catalyst design and subsequent attainment of prominent CO2RR activity in literature. This review tracks the evolution of the understanding of CO2RR active sites on different electrocatalysts such as metals, metal‐oxides, single atoms, metal‐carbon, and subsequently metal‐free carbon‐based catalysts. Despite the tremendous research efforts in the field, many scientific questions on the role of various active sites in governing CO2RR activity, selectivity, stability, and pathways are still unanswered. These gaps in knowledge are highlighted and a discussion is set forth on the merits of utilizing advanced in‐situ and operando characterization techniques and machine learning (ML). Using this technique, the underlying mechanisms can be discerned, and as a result new strategies for designing active sites may be uncovered. Finally, this review advocates an interdisciplinary approach to discover and design CO2RR active sites (rather than focusing merely on catalyst activity) in a bid to stimulate practical research for industrial application.

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Sulfur-Modulated Tin Sites Enable Highly Selective Electrochemical Reduction of CO2 to Formate

Cited by 429 publications

References 47 publications

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO₂ to Value‐Added Chemicals and Fuel

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Sulfur-Modulated Tin Sites Enable Highly Selective Electrochemical Reduction of CO2 to Formate

Cited by 429 publications

References 47 publications

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO2 Reduction to Formate

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO2 Reduction to Formate

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO2 to Value‐Added Chemicals and Fuel

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Product

Resources

About

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO₂ to Value‐Added Chemicals and Fuel