Mechanism of C–C bond formation in the electrocatalytic reduction of CO<sub>2</sub> to acetic acid. A challenging reaction to use renewable energy with chemistry

Genovese, Chiara; Ampelli, Claudio; Perathoner, Siglinda; Centi, Gabriele

doi:10.1039/c6gc03422e

Cited by 144 publications

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“…[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. [16,20] Herein, we report af acile strategy of catholyte-free electrocatalytic CO 2 reduction (CF-CO 2 R) that avoids the solubility limitation by supplying an appropriate amount of water vapor with gaseous CO 2 as acathode reactant. Even though some researchers investigated ad irect electroreduction of gaseous CO 2 to circumvent the solubility limitation, the FE towards formic acid was only 5% and the partial current density (PCD) of formate was very poor (< 0.5 mA cm À2 ).…”

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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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Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate

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“…Another interesting example to discussh ere regards the direct production of acetic acid by electrocatalytic reduction of CO 2 . [57] Acetic acid is al arge-volume chemical (about 14 Mt global annualp roduction), with interesting market dynamics, growing at ac ompound annual growth rate (CAGR) of around8 .5 %b etween 2016 and 2021. [57] Acetic acid is used in production of chemicalc ompounds such as purified terephthalic acid (PTA), vinyl acetate monomer (VAM), Acetate Esters, Acetic Anhydride.…”

Section: Re-driven Process/energy Intensificationmentioning

confidence: 99%

“…[57] Acetic acid is al arge-volume chemical (about 14 Mt global annualp roduction), with interesting market dynamics, growing at ac ompound annual growth rate (CAGR) of around8 .5 %b etween 2016 and 2021. [57] Acetic acid is used in production of chemicalc ompounds such as purified terephthalic acid (PTA), vinyl acetate monomer (VAM), Acetate Esters, Acetic Anhydride. Growing demandf or VAMc oupled with increasing demandf or purified PTAa nd ethyl acetate are the major factors driving the globalm arket for acetic acid.…”

Section: Re-driven Process/energy Intensificationmentioning

confidence: 99%

“…The electrolysis of the latter provides the H + /e À used in the reduction of CO 2 .T he reaction mechanism involves the reactiono ft he radical anion CCO 2 À with surface adsorbed CH 3 -like species derived from the reduction of adsorbed CO 2 . [57] There is rising interest in this electrocatalytic synthesis. [58] The important aspecti st hat, with respect to the multistep synthesis of acetic acid from fossil fuels, direct electrocatalytic synthesis allows to lower by af actor 5-6 the carbon footprint, owing to ac ombination of process intensificationa nd the uses of CO 2 as ar aw materiala nd of renewables ourceso fe nergy.…”

Section: Re-driven Process/energy Intensificationmentioning

confidence: 99%

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Beyond Solar Fuels: Renewable Energy‐Driven Chemistry

et al. 2017

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The ongoing energy transition based on the substitution of fossil feedstocksa se nergy sourcesw ith renewablee nergy (RE) sourcesdemands reconsideration of current industrial chemical production,w hich is anticipated to be at the end of this cycle. The main element determining greenhouse gas (GHG) emissions during chemical production is the use of fossil fuels to drive chemical transformations, rather than their use as sources of carbon.F urthermore, RE will become progressively cheaper as as ource of energy with respectt ot hat derived fromf ossil fuels and new chemical raw materials such as methanol, derived from the conversion of waste CO 2 ,w illb ecome available on al arge scale, being used as energy vectors to transport RE on ag lobals cale. There are thus converging sustainability elements indicating the need to move to af uture scenario of chemicali ndustrialp roduction denoted as "RE-driven chemistry", which can also provide ag reat opportunity for innovation and competitivity in chemical industry.I nt his Essay we discuss how it is realistic to conceive of RE-driven chemistry,w hich will be an on-incremental change to move to al ow-carbon economy,t hat is, with ad ecreasei nG HG emissions by up to 80 %. However,t his objective requires the fulfillment of two criteria: i) the use of RE-driven processes for the production of base raw materials, such as olefins,m ethanol, and ammonia,w hich are at the top of the chemical production value chain and ii)the development of RE-driven routes that simultaneously realize process and energy intensification, that is, which combine the use of RE in substitution of fossil fuels to significantly reducethe number of the process steps. Twospecific examples of using RE to realize novel conversion pathways are discussed: the direct synthesies of ammonia from N 2 andH 2 Oa nd that of acetic acid from CO 2 and H 2 O. They exemplify the above concept and the possibility of ar eductiono fo ver 80 % in GHG emissions. Some aspects of the production of olefins from renewable methanola re also discussed. Enabling this vision of an ew chemical industrial production based on the use of RE requires significant investment in new production technologies, because an on-incremental change in chemical industry-thedevelopment of newm aterials, reactors and processes( for example, based on the use of electrons and photons rather than heat as today)-is an ecessity.T hese novel technologiesw ill offer the opportunity to overcome the actual industrial process, by switching from largei ntegrated chemical plantst oad istributed modelo fp roduction with various sustainability benefits.

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“…Both electro-chemical and photo-electro-chemical reductions of carbon dioxide have been studied in detail and experiments conducted confirm their feasibility. [9][10][11][12][13][14][15][16] Electrochemical reduction (ECR) of carbon dioxide involves addition of protons and electrons to carbon dioxide resulting formation of hydrocarbons through the application of suitable voltage. Various possible CO 2 reduction reactions are shown in Table I.…”

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An Integrated Device for Converting Water, Carbon Dioxide and Light into Electricity and Organics

Yadav¹,

Basu²

2017

J. Electrochem. Soc.

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Global warming presents an ever-rising challenge to humans today, caused by an unprecedented rise in the carbon dioxide levels in the atmosphere over the past decade. This study proposes a way to fix this problem in a sustainable way using sunlight to convert CO 2 into useful fuels through a novel device. A Simulink model of photo-voltaic cell, CO 2 electrochemical reduction and photoelectrochemical reduction cell is developed and integrated together to model the device. The photo-voltaic cell model takes solar irradiation and temperature as inputs, giving electrical power as output. The CO 2 electrochemical reduction cell model consists of three blocks, anode, cathode and voltage. Mole balances on anode and cathode give the product flow-rates. Nernst and Butler-Volmer equations calculate the voltage required to operate the CO 2 reduction cell. The CO 2 photo-electrochemical reduction cell calculates product flow rates and voltage required to operate the cell using continuity, charge balance and Butler-Volmer equations. The model of the integrated device calculates i-V characteristics of the photovoltaic, electrochemical reduction and photo-electrochemical reduction cell under different environmental conditions, the product flow rates, contribution of various cell over-voltages. The model developed predicts photo-electrochemical route to be more energy and area efficient as compared to the electrochemical route. With the fast depletion of non-renewable energy sources e.g., fossil fuels and environmental pollution caused by their combustion, there is not only an increasing need to look for alternative sources of energy but also fix the disproportionately harmful amount of greenhouse gases in the atmosphere. Carbon dioxide forms a major portion of greenhouse gas emissions, responsible for global warming. It is released into the atmosphere by natural and man-made causes, with emissions from human activities being 100 times greater than those from natural causes. Increasingly, there are efforts to consider carbon dioxide as a resource for commercial opportunity rather than a waste by incurring a low cost of disposal.1,2,3 Commercially viable and pure CO 2 is available from current and future plants for carbon sequestration and storage (CSS).3 Moreover, chemical recycling of carbon dioxide is gaining importance as CSS option is unavailable for many emission sites and also, in cases where concentration of carbon dioxide in emissions is dilute, and hence, commercially inviable for CCS. About 5-10% of worldwide CO 2 emissions, which were approximately 46 Gt in 2016, could find potential use in the production of fuels and chemicals. This is one order of magnitude higher than present use of CO 2 in industry. 4 Currently, carbon dioxide is put to use in the production of urea, methanol, metal carbonates, bi-carbonates and plastics.5 Converting CO 2 to fuels offers better economic advantage owing to their greater market demand and high prices. Certain fuels like methanol, ethanol can also serve as feedstock for fuel cells p...

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Mechanism of C–C bond formation in the electrocatalytic reduction of CO₂ to acetic acid. A challenging reaction to use renewable energy with chemistry

Abstract: A study on the mechanism of C–C bond formation in the electrocatalytic reduction of CO2 to acetic acid with Cu/CNT electrocatalysts.

Cited by 144 publications

References 48 publications

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate

Beyond Solar Fuels: Renewable Energy‐Driven Chemistry

An Integrated Device for Converting Water, Carbon Dioxide and Light into Electricity and Organics

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Mechanism of C–C bond formation in the electrocatalytic reduction of CO2 to acetic acid. A challenging reaction to use renewable energy with chemistry

Abstract: A study on the mechanism of C–C bond formation in the electrocatalytic reduction of CO2 to acetic acid with Cu/CNT electrocatalysts.

Cited by 144 publications

References 48 publications

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

Beyond Solar Fuels: Renewable Energy‐Driven Chemistry

An Integrated Device for Converting Water, Carbon Dioxide and Light into Electricity and Organics

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Mechanism of C–C bond formation in the electrocatalytic reduction of CO₂ to acetic acid. A challenging reaction to use renewable energy with chemistry

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate

Catholyte‐Free Electrocatalytic CO₂ Reduction to Formate