Nitrogen‐Doped Carbon Polyhedrons Confined Fe–P Nanocrystals as High‐Efficiency Bifunctional Catalysts for Aqueous Zn−CO₂ Batteries

Abstract

Emerging Fe bonded with heteroatom P in carbon matrix (FePC) holds great promise for electrochemical catalysis, but the design of highly active and cost‐efficient FePC structure for the electrocatalytic CO2 reduction reaction (CO2RR) and aqueous ZnCO2 batteries (ZCBs) is still challenging. Herein, polyhedron‐shaped bifunctional electrocatalysts, FeP nanocrystals anchored in N‐doped carbon polyhedrons (Fe‐P@NCPs), toward a reversible aqueous ZnCO2 battery, are reported. The Fe‐P@NCPs are synthesized through a facile strategy by using self‐templated zeolitic imidazolate frameworks (ZIFs), followed by an in situ high‐temperature calcination. The resultant catalysts exhibit aqueous CO2RR activity with a CO Faradaic efficiency up to 95% at −0.55 V versus reversible hydrogen electrode (RHE), comparable to the previously best‐reported values of FeNC structure. The as‐constructed ZCBs with designed Fe‐P@NCPs cathode, show the peak power density of 0.85 mW cm−2 and energy density of 231.8 Wh kg−1 with a cycling durability over 500 cycles, and outstanding stability in terms of discharge voltage for 7 days. The high selectivity and efficiency of the battery are attributed to the presence of highly catalytic FeP nanocrystals in N‐doped carbon matrix, which can effectively increase the number of catalytically active sites and interfacial charge–transfer conductivity, thereby improving the CO2RR activity.

Bifunctional Nb-N-C atomic catalyst for aqueous Zn-air battery driving CO2 electrolysis

“…The electrochemical CO 2 and O 2 reduction reactions (CO 2 RR and ORR) are two fundamental reactions for CO 2 capturing and renewable energy supplying, which not only address global warming and energy crises but also enable the generation of valuable products [1][2][3][4][5]. However, designing multifunctional electrocatalysts for supplying renewable electricity and simultaneously converting CO 2 to value-added products (such as CO, HCOOH, C 2 H 4 , and CH 4 ) is still a significant challenge [6][7][8][9][10][11][12][13]. Generally, designing efficient and economically viable bifunc-tional electrocatalysts is regarded as a promising method for integrating CO 2 RR and ORR activities [14,15].…”

Bifunctional BiPd Alloy Particles Anchored on Carbon Matrix for Reversible Zn–CO2 Battery

“…Excessive consumption of fossil energy resources and CO 2 accumulation urge our society to develop eco-friendly strategies for tackling CO 2 accumulation and energy issues. , Among them, electrochemical carbon dioxide reduction reaction (CO 2 RR), metal–CO 2 battery, and Zn–air battery (ZAB) have been demonstrated as efficient strategies for energy conservation and supply. − The electrochemical CO 2 RR process is capable of transforming gaseous CO 2 into C 1 and C 2 products (such as CO, HCOOH, CH 4 , C 2 H 4 , and C 2 H 5 OH). − Various electrochemical CO 2 RR products can be achieved depending on the electrocatalytic species, for instance, efficient Cu-based catalysts for C 1–3 generation, transition-metal-nitrogen coordinated catalysts for CO formation, Bi-based catalysts for HCOOH production, and so on. − These regulations of coordination structure overcome the high CO dissociation energy of CO 2 and deal with the unsatisfactory inherently sluggish kinetics of CO 2 RR . Moreover, the aqueous zinc batteries are applied extensively, attributed to their high safety, lower cost, and high theoretical capacity of zinc (820 mA h g –1 ). − The discharge process of ZAB can be assumed that zinc electrode dissolution drives cathodic ORR along with anodic Zn metal forming zincate ions (Zn­(OH) 4 2– ) and further decomposing to insoluble zinc oxide (ZnO).…”

“…Unlike other kinds of battery systems, ZCBs are inclined to transform CO 2 into value-added chemical production instead of providing electricity . For instance, the as-constructed aqueous ZCB enables independently converting CO 2 to HCOOH/CO via proton-coupled electron transfer without extra power inputs. , Although many pioneering reports have been proposed for ZCB converting CO 2 to CO, there still exist great challenges for reversible CO 2 –HCOOH interconversion based on ZCB. ,− …”

Oxygen Vacancy-Rich Amorphous Copper Oxide Enables Highly Selective Electroreduction of Carbon Dioxide to Ethylene

“…3c), which gives a value of 147 mV•dec −1 for m-CuOx. This value is obviously smaller than that of c-Cu2O (290 mV•dec −1 ), implying the faster ECR kinetics of m-CuOx in comparison with c-Cu2O [47][48][49][50] .…”