Analysis on the effect of operating conditions on electrochemical conversion of carbon dioxide to formic acid

Kim, Hak Yoon; Choi, Insoo; Ahn, Sang Hyun; Hwang, Seung Jun; Yoo, Sung Jong; Han, Jonghee; Kim, Jihyun; Park, Hansoo; Jang, Jong Hyun; Kim, Soo Kil

doi:10.1016/j.ijhydene.2014.03.145

Cited by 78 publications

(55 citation statements)

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“…[1] In recent years, there has been a massive increase in research on CO 2 RR, mostly focusing on catalyst development, [2][3][4][5][6] but also on electrode design, [7,8] electrolyte composition [9,10] and reaction engineering. [11,12] The most typical reactions that can occur in a CO 2 saturated aqueous electrolyte are listed below. Depending on the catalyst, different reactions are favored.…”

Section: Introductionmentioning

confidence: 99%

“…Most groups report an optimum in FE at rather low temperatures between 0°C and 35°C with HER becoming increasingly predominant as CO 2 solubility drops with increasing temperature. [12,15,55,56] In contrast to CO 2 solubility, diffusion coefficient rises with temperature, which should lead to a maximum in performance at an optimum temperature. Both effects are depicted in Figure 2.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO₂ Reduction Reaction

et al. 2019

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A detailed investigation of the influence of operating temperature on the electrochemical reduction of CO2 to formate at tin oxide loaded gas diffusion electrodes (GDEs). Ambient pressure electrolysis is performed between 20 and 70 °C with a focus on maximizing current density and energy efficiency while maintaining an average formate faradaic efficiency of at least 80 %. The best performance is achieved at a temperature of 50 °C, which allows a current density of 1000 mA cm−2. Lower or higher temperatures both show an increased hydrogen evolution at said current density. Further investigation of CO2 transport limitation revealed a minimum at 50 °C, which is explained by the opposing influence of temperature on CO2 diffusion coefficients and solubility. This explanation is supported by an estimate of the current density at which hydrogen evolution starts to increase based on the flooded agglomerate model. Long‐term operation for 24 h also revealed an optimum temperature of 50 °C, which helps to suppress the increasing rate of hydrogen evolution and with that a mechanical degradation of the GDE.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO₂ Reduction Reaction

et al. 2019

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“…CO 2 is an attractive building block for C 1 -chemistry; however, the conversion of CO 2 is quite challenging due to its inert and stable nature. Several methods for the activation and conversion of CO 2 have been proposed, such as chemical [5], biological [6], photochemical [7,8], and electrochemical methods [9][10][11][12]. Among these technologies, the electrochemical method is the most promising and benign, owing to its convenient operation and ability to control the yield and selectivity of the produced chemicals.…”

Section: Introductionmentioning

confidence: 99%

“…Various lowcarbon species are generated during this process, e.g., HCOOH [11,[13][14][15], CH 4 [9,16], CO [17][18][19], and C 2 H 4 [20]. When a simultaneous hydrogen evolution reaction (HER) occurs, CO/H 2 mixture (syngas) can be produced in a single electrochemical cell [11,14]. This strategy has drawn great attention because the syngas can be utilized and transformed into other valuable chemicals such as methanol and ethanol via the Fischer-Tropsch process.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of M-MOF-74 (M=Co, Ni, Zn) and its Application as an ElectroCatalyst for Electrochemical CO₂ Conversion and H₂ Production

Choi

Jung

Yoo

et al. 2017

Journal of Electrochemical Science and Technology

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Electrochemical conversion of CO 2 and production of H 2 were attempted on a three-dimensionally ordered, porous metal organic framework (MOF-74) in which transition metals (Co, Ni, and Zn) were impregnated. A lab-scale proton exchange membrane-based electrolyzer was fabricated and used for the reduction of CO 2 . Real-time gas chromatography enabled the instantaneous measurement of the amount of carbon monoxide and hydrogen produced. Comprehensive calculations, based on electrochemical measurements and gaseous product analysis, presented a time-dependent selectivity of the produced gases. M-MOF-74 samples with different central metals were successfully obtained because of the simple synthetic process. It was revealed that Co-and Ni-MOF-74 selectively produce hydrogen gas, while Zn-MOF-74 successfully generates a mixture of carbon monoxide and hydrogen. The results indicated that M-MOF-74 can be used as an electrocatalyst to selectively convert CO 2 into useful chemicals.

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“…[1,[21][22][23] In particular, for the Sn electrode,t he FE of formate decreased with an increasing temperature above 293 K. [23,24] We examined the electrolytic performances of CF-CO 2 Rb yi ncreasing the reaction temperature to confirm that the solubility constraint could be overcome at ac ell voltage of 2.2 Vw ith ac onstant vapor supply of 12.58 mg min À1 cm À2 .F igure 1A (and Supporting Information, Figure S5) shows the FE of formate in the CF-CO 2 Ra safunction of cell temperature compared to that in the conventional CO 2 Ru sing a1m KCl catholyte.A s expected, in the conventional CO 2 R, the FE of formate decreased drastically from 66.7 %to22.6 %with an increasing cell temperature from 303 Kto363 K. On the other hand, the FEs in the CF-CO 2 Rw ere more than 90 %u pt o3 43 K, and 84.8 %e ven at 363 K( Figure 1A). [1,[21][22][23] In particular, for the Sn electrode,t he FE of formate decreased with an increasing temperature above 293 K. [23,24] We examined the electrolytic performances of CF-CO 2 Rb yi ncreasing the reaction temperature to confirm that the solubility constraint could be overcome at ac ell voltage of 2.2 Vw ith ac onstant vapor supply of 12.58 mg min À1 cm À2 .F igure 1A (and Supporting Information, Figure S5) shows the FE of formate in the CF-CO 2 Ra safunction of cell temperature compared to that in the conventional CO 2 Ru sing a1m KCl catholyte.A s expected, in the conventional CO 2 R, the FE of formate decreased drastically from 66.7 %to22.6 %with an increasing cell temperature from 303 Kto363 K. On the other hand, the FEs in the CF-CO 2 Rw ere more than 90 %u pt o3 43 K, and 84.8 %e ven at 363 K( Figure 1A).…”

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confidence: 99%

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate

et al. 2018

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Electrochemical reduction of carbon dioxide (CO 2 ) into value-added chemicals is ap romising strategy to reduce CO 2 emission and mitigate climate change.O ne of the most serious problems in electrocatalytic CO 2 reduction (CO 2 R) is the lows olubility of CO 2 in an aqueous electrolyte,w hich significantly limits the cathodic reaction rate.T his paper proposes af acile method of catholyte-free electrocatalytic CO 2 reduction to avoid the solubility limitation using commercial tin nanoparticles as acathode catalyst. Interestingly,as the reaction temperature rises from 303 Kto363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm À2 ,despite the decrease in CO 2 solubility. Furthermore,asignificantly high formate concentration of 41.5 gL À1 is obtained as aone-path product at 343 Kwith high PCD (51.7 mA cm À2 )and high Faradaic efficiency (93.3 %) via continuous operation in afull flowcell at alow cell voltage of 2.2 V.The electrocatalytic CO 2 reduction (CO 2 R) into useful chemicals or fuels has attracted significant interest for renewable energy storage and environmental sustainability. [1][2][3][4] There are several electrochemical pathways to convert CO 2 into valuable products, [1,5,6] among which formic acid or formate has received particular attention over the past few years because the CO 2 Ri nto formic acid is regarded as as uitable reaction for industrial scale production. [7][8][9] However,there still remain some problems to be solved, including alarge overpotential, low Faradaic efficiency(FE), and poor stability of electrocatalysts.Inparticular, the low solubility of CO 2 in the catholyte significantly limits the reaction rate,thus greatly hindering the large-scale application of the CO 2 R. [1] Furthermore,t he liquid electrolytes dilute the reduction products,w hich increases the separation costs for product recovery.Some efforts have been reported to overcome the solubility limitation and enhance the current density of formate production, including development of ah ighly porous structure of SnO 2 ,t unable alloys,a nd ionic liquids (ILs). [2,[10][11][12][13] Despite these significant results,t heir kinetics of CO 2 Rconversion into formate is still limited by the low CO 2 concentration in electrolytes.I nr ecent years,s ome research groups reported remarkable improvement in the current density of CO 2 Rt of ormate using gas diffusion electrodes (GDEs) with metal nanoparticles. [5,[14][15][16][17][18][19] This type of electrode provides at hree-phase interface of gas/ electrolyte/ catalyst, in which the CO 2 molecules only have to diffuse through av ery thin liquid layer of electrolyte to reach the catalyst surface. [19] Castillo et al. [5] achieved ah igh formate concentration of 2.5 gL À1 via continuous operation of a10cm 2 filterpress cell using Sn-GDEs under galvanostatic condition of 150 mA cm À2 .A lthough they obtained an enhanced performance over previous results,their method still suffered from ahigh cell voltage of 3.7 V, alow FE of 70 %, and t...

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Analysis on the effect of operating conditions on electrochemical conversion of carbon dioxide to formic acid

Cited by 78 publications

References 35 publications

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO₂ Reduction Reaction

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO₂ Reduction Reaction

Facile Synthesis of M-MOF-74 (M=Co, Ni, Zn) and its Application as an ElectroCatalyst for Electrochemical CO₂ Conversion and H₂ Production

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate

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Analysis on the effect of operating conditions on electrochemical conversion of carbon dioxide to formic acid

Cited by 78 publications

References 35 publications

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO2 Reduction Reaction

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO2 Reduction Reaction

Facile Synthesis of M-MOF-74 (M=Co, Ni, Zn) and its Application as an ElectroCatalyst for Electrochemical CO2 Conversion and H2 Production

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

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Product

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Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO₂ Reduction Reaction

Influence of Temperature on the Performance of Gas Diffusion Electrodes in the CO₂ Reduction Reaction

Facile Synthesis of M-MOF-74 (M=Co, Ni, Zn) and its Application as an ElectroCatalyst for Electrochemical CO₂ Conversion and H₂ Production

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate