Electrocatalytic Reduction of CO
            <sub>2</sub>
            in Methanol Medium

Murugananthan, Muthu; Kaneco, Satoshi; Katsumata, Hideyuki; Suzuki, Tohru; Lad, Bhupesh Kumar

doi:10.1002/9781118831922.ch7

Cited by 7 publications

(5 citation statements)

References 45 publications

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“…In the future, we think that it will be also worthwhile to use nonaqueous electrolytes such as organic solvents or ionic liquids for CO 2 reduction on the copper-hydride clusters. As demonstrated experimentally, these nonaqueous electrolytes can supply protons in two ways: (1) by mixing a low concentration (∼100 ppm) of water in the organic or ionic liquid electrolyte; (2) by using a protic solvent such as methanol . In addition, the lattice-hydride mechanism of CO 2 reduction can be a general pathway beyond the Cu clusters, given the recent success in synthesizing other hydride-containing transition-metal clusters. , …”

Section: Resultsmentioning

confidence: 99%

Lattice-Hydride Mechanism in Electrocatalytic CO₂ Reduction by Structurally Precise Copper-Hydride Nanoclusters

et al. 2017

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Copper electrocatalysts can reduce CO to hydrocarbons at high overpotentials. However, a mechanistic understanding of CO reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as CuHL (L is a dithiophosphate ligand), offer unique selectivity for electrocatalytic CO reduction at low overpotentials. Our density functional theory (DFT) calculations predict that the presence of the negatively charged hydrides in the copper cluster plays a critical role in determining the selectivity of the reduction product, yielding HCOOH over CO with a lower overpotential. The HCOOH formation proceeds via the lattice-hydride mechanism: first, surface hydrides reduce CO to HCOOH product, and then the hydride vacancies are readily regenerated by the electrochemical proton reduction. DFT calculations further predict that hydrogen evolution is less competitive than HCOOH formation at the low overpotential. Confirming the predictions, electrochemical tests of CO reduction on the CuHL cluster demonstrate that HCOOH is indeed the main product at low overpotential, while H production dominates at higher overpotential. The unique selectivity afforded by the lattice-hydride mechanism opens the door for further fundamental and applied studies of electrocatalytic CO reduction by copper-hydride nanoclusters and other metal nanoclusters that contain hydrides.

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Section: Resultsmentioning

confidence: 99%

Lattice-Hydride Mechanism in Electrocatalytic CO₂ Reduction by Structurally Precise Copper-Hydride Nanoclusters

et al. 2017

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“…Methanol (Chang and Rousseau, 1985;Naitoh et al, 1993;Mizuno et al, 1995;Ortiz et al, 1995;Saeki et al, 1995aSaeki et al, , 1995b1996;Mizuno et al, 1997;Eggins et al, 1997;Kaneco et al, 1998aKaneco et al, , 1998bKaneco et al, , 1998c1999a, 1999b, 1999c2002;2006a, 2006b, 2006c2007a;2007b;Mizuno et al, 1998;Ohta et al, 1998;Kö leli, 2002, 2004;Ohya et al, 2009;Murugananthan et al, 2015;Albo and Irabien, 2016) 151 G 11 0.551 32.7 79.5 Recommended/ problematic standard reference potential can differ between the utilized solvents (Lewenstam and Scholz, 2013), e.g., for an Ag/Ag + RE, a constant reference point is not given and the measured potentials cannot be compared between the solvents. This is especially relevant because the product distribution can be highly dependent on the applied potential (Ito et al, 1985) and current density.…”

Section: Hazardousmentioning

confidence: 99%

“…As a protic solvent with a pK a value only slightly higher than that of water (pK a (MeOH) = 17.2, pK a (H 2 O) = 14.0, Izutsu, 2002), the reaction products observed in the CO 2 RR with MeOH are similar to those in aqueous solvents. At Cu electrodes, hydrocarbons and alcohols including methane, ethylene, and ethanol are formed (Naitoh et al, 1993;Mizuno et al, 1995;Mizuno et al, 1997;Kaneco et al, 1999aKaneco et al, , 1999bKaneco et al, , 1999c2002;2006a, 2006b, 2006c2007b;2007a;Ohya et al, 2009;Murugananthan et al, 2015). Similarly, metals included in the CO-generating group, such as Ag (Saeki et al, 1996;Kaneco et al, 1998aKaneco et al, , 1998bKaneco et al, , 1998c, Zn (Saeki et al, 1996), and Au (Kaneco et al, 1998a(Kaneco et al, , 1998b(Kaneco et al, , 1998c, also produce predominantly CO in MeOH-based electrolytes.…”

Section: àmentioning

confidence: 99%

Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO2

et al. 2019

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Different electrolytes applied in the aqueous electrocatalytic CO 2 reduction reaction (CO 2 RR) considerably influence the catalyst performance. Their concentration, species, buffer capacity, and pH value influence the local reaction conditions and impact the product distribution of the electrocatalyst. Relevant properties of prospective solvents include their basicity, CO 2 solubility, conductivity, and toxicity, which affect the CO 2 RR and the applicability of the solvents. The complexity of an electrochemical system impedes the direct correlation between a single parameter and cell performance indicators such as the Faradaic efficiency; thus the effects of different electrolytes are often not fully comprehended. For an industrial application, a deeper understanding of the effects described in this review can help with the prediction of performance, as well as the development of scalable electrolyzers. In this review, the application of supporting electrolytes and different solvents in the CO 2 RR reported in the literature are summarized and discussed.

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“…Despite methanol's promise for high solubility in CO 2 reduction, there have been limited literature reports using methanol solvent for electrochemical CO 2 conversion. [7] In general, reduction of CO 2 in methanol on metal cathodes has shown qualitatively similar selectivity to related aqueous systems but with higher selectivity towards formic acid and lower selectivity towards hydrogen. [8] Several reports of electrochemical reduction [8b,9] and homogeneous hydrogenation [10] of CO 2 in methanol have demonstrated the synthesis of a novel C 2 product, methyl formate (HCOOCH 3 ), largely replacing selectivity to formic acid (HCOOH), the more common product in aqueous media.…”

Section: Introductionmentioning

confidence: 99%

The pH and Potential Dependence of Pb‐Catalyzed Electrochemical CO₂ Reduction to Methyl Formate in a Dual Methanol/Water Electrolyte

et al. 2022

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The conversion of waste CO2 to value‐added chemicals through electrochemical reduction is a promising technology for mitigating climate change while simultaneously providing economic opportunities. The use of non‐aqueous solvents like methanol allows for higher CO2 availability and novel products. In this work, the electrochemistry of CO2 reduction in acidic methanol catholyte at a Pb working electrode was investigated while using a separate aqueous anolyte to promote a sustainable water oxidation half‐reaction. The selectivity among methyl formate (a product unique to reduction of CO2 in methanol), formic acid, and formate was critically dependent on the catholyte pH, with higher pH conditions leading to formate and low pH favoring methyl formate. The potential dependence of the product distribution in acidic catholyte was also investigated, with a faradaic efficiency for methyl formate as high as 75 % measured at −2.0 V vs. Ag/AgCl.

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Electrocatalytic Reduction of CO ₂ in Methanol Medium

Cited by 7 publications

References 45 publications

Lattice-Hydride Mechanism in Electrocatalytic CO₂ Reduction by Structurally Precise Copper-Hydride Nanoclusters

Lattice-Hydride Mechanism in Electrocatalytic CO₂ Reduction by Structurally Precise Copper-Hydride Nanoclusters

Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO2

The pH and Potential Dependence of Pb‐Catalyzed Electrochemical CO₂ Reduction to Methyl Formate in a Dual Methanol/Water Electrolyte

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Electrocatalytic Reduction of CO 2 in Methanol Medium

Cited by 7 publications

References 45 publications

Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters

Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters

Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO2

The pH and Potential Dependence of Pb‐Catalyzed Electrochemical CO2 Reduction to Methyl Formate in a Dual Methanol/Water Electrolyte

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Product

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Electrocatalytic Reduction of CO ₂ in Methanol Medium

Lattice-Hydride Mechanism in Electrocatalytic CO₂ Reduction by Structurally Precise Copper-Hydride Nanoclusters

Lattice-Hydride Mechanism in Electrocatalytic CO₂ Reduction by Structurally Precise Copper-Hydride Nanoclusters

The pH and Potential Dependence of Pb‐Catalyzed Electrochemical CO₂ Reduction to Methyl Formate in a Dual Methanol/Water Electrolyte