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

Abstract

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.

Electrochemical Fixation of Carbon Dioxide in Molten Salts on Liquid Zinc Cathode to Zinc@Graphitic Carbon Spheres for Enhanced Energy Storage

“…Excessive emission of carbon dioxide (CO 2 ) is a threat to the ecological balance. [1][2][3][4][5] CO 2 is also an exploitable carbon and oxygen resource. [6][7][8][9][10][11][12] Fixation of CO 2 into valuable chemicals could simultaneously realize carbon reduction and reutilization of CO 2.…”

Continuous Electrochemical Reduction of CO2 to Formate: Comparative Study of the Influence of the Electrode Configuration with Sn and Bi-Based Electrocatalysts

“…Furthermore, this product has been recommended as an interesting fuel for low-temperature fuel cells [ 30 , 31 ], as well as a promising hydrogen carrier [ 32 , 33 ]. According to the literature [ 22 , 34 , 35 ], electrocatalysts of different nature, different electrode configurations, and different electrochemical reactors have been used for studying the electrocatalytic reduction of CO 2 to HCOOH/HCOO − . On the one hand, copper (Cu) [ 36 ], cobalt (Co) [ 37 ], molybdenum (Mo) [ 38 ], lead (Pb) [ 39 , 40 , 41 ], indium (In) [ 42 , 43 , 44 ], palladium (Pd) [ 45 , 46 ], and especially tin (Sn) [ 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 ] and bismuth (Bi) [ 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 ] are the most common catalysts investigated for the selective electrochemical reduction of CO 2 to HCOOH/HCOO − .…”

An efficient method to prepare supported bismuth nanoparticles as highly selective electrocatalyst for the conversion of CO2 into formate

“…The state-of-the-art electrocatalysts for the conversion of CO 2 into formate are typically based on main group metals such as Sn, Pb, Bi and In. 9 It has been proposed that these metals promote the adsorption of CO 2 with subsequent formation of the *OCOH over the *COOH intermediate on the catalyst surface. The *OCOH intermediate is generally recognised as the precursor to the formation of formate as product of CO 2 reduction.…”

“…The *OCOH intermediate is generally recognised as the precursor to the formation of formate as product of CO 2 reduction. 9 Experimental evidences suggest that an oxide layer that tends to form at the surface of main group metals has a central role in defining their catalytic properties. 9 Among these metals, Bi is particularly appealing for the low cost, low toxicity and low environmental hazard.…”

“…9 Experimental evidences suggest that an oxide layer that tends to form at the surface of main group metals has a central role in defining their catalytic properties. 9 Among these metals, Bi is particularly appealing for the low cost, low toxicity and low environmental hazard. Bibased electrocatalysts have been prepared through the reduction of Bi 3+ precursors via chemical, 10-14 electrochemical [15][16][17][18][19][20][21][22][23] or hydrothermal [24][25][26][27] methods (Table S1, S2 and Fig.…”