Insights into the Composition and Function of a Bismuth-Based Catalyst for Reduction of CO<sub>2</sub> to CO

Atifi, Abderrahman; Keane, Thomas P.; DiMeglio, John L.; Pupillo, Rachel C.; Mullins, David R.; Lutterman, Daniel A.; Rosenthal, Joel

doi:10.1021/acs.jpcc.9b00504

Cited by 24 publications

(18 citation statements)

References 44 publications

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“…These observations are consistent with Dy partitioning between water-coordinated and IL-coordinated speciation. A similar impact of ionic liquids solvation and coordination on the redox behavior of organic and inorganic systems and their implications in many electrochemical processes have been extensively reported by Atifi et al − At an equimolar fraction, the water molecules would be partially coordinated to the Dy complex (Red1), with an important fraction remaining as free or weakly coordinated molecules. Increasing the metal loading (or lowering x H 2 O ) increased the fraction of metal-coordinated water (Dy-H 2 O) at the expense of free or weakly coordinated water (IL-coordinated complex), resulting in a rise of Red1 at the expense of Red2.…”

Section: Resultssupporting

confidence: 65%

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

Orme

Baek

Fox

et al. 2021

ACS Sustainable Chem. Eng.

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The electrochemical production of rare earth metals (REMs) in ionic liquids (ILs) has received much attention as a promising, sustainable replacement to molten salt electrolysis. Water additives have been suggested as a promoting strategy for the ionic liquid process; however, the fundamental understanding of the interfacial processes required to assess the overall viability for REM production is lacking. In this regard, a full investigation of the impact of water on dysprosium (Dy) electrodeposition in pyrrolidinium triflate (BMPyOTf) ionic liquid was carried out. Water introduction was revealed to involve an interplay of implications on the electrodeposition process, including coordination, speciation, reduction pathways, interfacial dynamics, nucleation, and metal stability and purity. Under highly dry conditions, the reduction occurs at a very negative potential (−3.3 V) in a consecutive pathway, resulting in negligible metal electrodeposition (low rate and efficiency) at the electrode surface. Small water concentrations (<500 ppm) lead to partitioning of the Dy complex between water and IL-coordinated speciation, giving rise to an additional wave at a more positive potential (−2.4 V). Probing the heterogeneous Dy speciation by spectroscopic analyses enabled uncovering of the reduction mechanism and evaluation of the mass transport properties. In addition to lowering the reduction thermodynamics, water introduction also improved the nucleation, deposition rate, and faradic efficiency. Despite these benefits, stripping voltammetric analysis predicts substantial chemical reactivity of the deposited Dy metal with water additives and/or electrolyte components, under long timescales. Surface characterization of the obtained product confirmed the instability of Dy metal as an oxidized/fluorinated material and its limited purity (∼60%). Moreover, high water introduction triggered a fast hydrogen evolution reaction (HER), downgrading the robustness of system efficiency. The overall impact of water additives seems to engender both promoting and mitigating effects on electrochemical REM production in IL, requiring a specific technoeconomic assessment and/or more innovative strategies to be sought.

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Section: Resultssupporting

confidence: 65%

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

Orme

Baek

Fox

et al. 2021

ACS Sustainable Chem. Eng.

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“…There are several reports on the carbon monoxide (CO) production in ionic liquid electrolyte by using Bi‐based materials. [ 23–26 ] However, ERC is more appealing in aqueous solution for practical application. Recently, some efforts have been dedicated to the HCOOH (or HCOO − ) production in aqueous solution over Bi‐based catalysts.…”

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confidence: 68%

Efficient CO₂ Reduction to HCOOH with High Selectivity and Energy Efficiency over Bi/rGO Catalyst

et al. 2020

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have been dedicated to produce HCOOH (or HCOO − ) through ERC. Several metals, such as Pd, Pb, Hg, In, and Cd, exhibit good selectivity for HCOOH, while some of them are plagued by the shortcomings of scarcity, high cost or toxicity. [19][20][21][22] Besides, many catalysts exhibit low cathodic energy efficiency (EE), indicating the large energy consumption, because of the high overpotential and low Faradaic efficiency (FE) of products. [14] Therefore, developing the resource-abundant catalysts with high FE and low overpotential to increase EE is significant while still very challenging.Theoretically, Bi might be an intriguing catalyst for ERC as it is ecofriendly, costeffective, and inferior for H 2 evolution. There are several reports on the carbon monoxide (CO) production in ionic liquid electrolyte by using Bi-based materials. [23][24][25][26] However, ERC is more appealing in aqueous solution for practical application. Recently, some efforts have been dedicated to the HCOOH (or HCOO − ) production in aqueous solution over Bi-based catalysts. [27][28][29][30][31] Moreover, Bi shows a relatively positive electrode potential, which is conducive to obtain the high cathodic EE and long-term stability. Thus, it is desired to improve Bi-based catalysts with high selectivity and cathodic EE for HCOOH production in aqueous solution.Herein, the ultrafine Bi nanoparticles (NPs) anchored on reduced graphene oxide (Bi/rGO) is synthesized and employed for ERC in 0.1 m KHCO 3 electrolyte. As a result, the synthesized Bi/rGO endows the ERC with excellent performance under normal pressure and room temperature. It almost outperforms all recently reported electrocatalysts with the highest 98% FE and meanwhile a high cathodic EE of 71% for HCOOH at −0.8 V versus RHE (the voltages reported here are against RHE unless noted), which is also comparable with the most existing catalysts for the HCOOH production. Moreover, the obtained FE of HCOOH and current density show negligible deterioration over 12 h, illustrating the favorable stability of Bi/ rGO.Bi/rGO is synthesized through a facile reduction route by using a reducing agent of sodium borohydride. For comparison, pure Bi and Bi-PVP using the polyvinylpyrrolidone (PVP) as the dispersant are also prepared as well. As shown in Figure 1a, the diffraction peaks of all three samples can be assigned to metallic Bi (JCPDS: 44-1246). [32] Additionally, high-resolution X-ray photoelectron spectroscopy (XPS) spectra (Figure 1b) also manifest that only Bi metal exists in all samples. The Bi 4f signals at 156.8 and 162.1 eV for Bi-PVP and pure Bi are in the The electroreduction of carbon dioxide (CO 2 ) to value-added fuels is of great significance to meet the ever-increasing energy and environmental challenges. So far, desirable selectivity and Faradaic efficiency for CO 2 reduction can be obtained over most electrocatalysts. However, improving cathodic energy efficiency is still neglected in research. Herein, a facile reduction method is first presented to synthesize the ultrafine non-n...

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“…Homogeneous molecular catalysts that work as efficient ECR catalysts at the molecular level have been well summarized in previous reports [35–38] . Heterogeneous 0D metal nanoparticles, including Au, [39–45] Ag, [46–48] Pt, [49, 50] Bi, [51, 52] and Cu [53–56] etc., have been intensively investigated for ECR. Some recently reported advances of 0D nanoparticles for CDRR are listed in Table 1.…”

Section: Nanostructured Materials As Catalysts For Cdrrmentioning

confidence: 97%

Nanostructures for Electrocatalytic CO₂ Reduction

Ouyang

Huang

Wang

et al. 2020

Chemistry A European J

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One of the most effective ways to cope with the problems of global warming and the energy shortage crisis is to develop renewable and clean energy sources. To achieve a carbon‐neutral energy cycle, advanced carbon sequestration technologies are urgently needed, but because CO2 is a thermodynamically stable molecule with the highest carbon valence state of +4, this process faces many challenges. In recent years, electrochemical CO2 reduction has become a promising approach to fix and convert CO2 into high‐value‐added fuels and chemical feedstock. However, the large‐scale commercial use of electrochemical CO2 reduction systems is hindered by poor electrocatalyst activity, large overpotential, low energy conversion efficiency, and product selectivity in reducing CO2. Therefore, there is an urgent need to rationally design highly efficient, stable, and scalable electrocatalysts to alleviate these problems. This minireview also aims to classify heterogeneous nanostructured electrocatalysts for the CO2 reduction reaction (CDRR).

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Insights into the Composition and Function of a Bismuth-Based Catalyst for Reduction of CO₂ to CO

Cited by 24 publications

References 44 publications

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

Efficient CO₂ Reduction to HCOOH with High Selectivity and Energy Efficiency over Bi/rGO Catalyst

Nanostructures for Electrocatalytic CO₂ Reduction

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Insights into the Composition and Function of a Bismuth-Based Catalyst for Reduction of CO2 to CO

Cited by 24 publications

References 44 publications

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

Efficient CO2 Reduction to HCOOH with High Selectivity and Energy Efficiency over Bi/rGO Catalyst

Nanostructures for Electrocatalytic CO2 Reduction

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Product

Resources

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Insights into the Composition and Function of a Bismuth-Based Catalyst for Reduction of CO₂ to CO

Efficient CO₂ Reduction to HCOOH with High Selectivity and Energy Efficiency over Bi/rGO Catalyst

Nanostructures for Electrocatalytic CO₂ Reduction