Nanostructures for Electrocatalytic CO2 Reduction

One of the most effective ways to cope with the problems of global warming and the energy shortage crisis is to develop renewable and clean energy sources. To achieve a carbon-neutral energy cycle, advanced carbon sequestration technologies are urgently needed, but because CO₂ is a thermodynamically stable molecule with the highest carbon valence state of +4, this process faces many challenges. In recent years, electrochemical CO₂ reduction has become a promising approach to fix and convert CO₂ into high-value-added fuels and chemical feedstock. However, the large-scale commercial use of electrochemical CO₂ reduction systems is hindered by poor electrocatalyst activity, large overpotential, low energy conversion efficiency, and product selectivity in reducing CO₂. Therefore, there is an urgent need to rationally design highly efficient, stable, and scalable electrocatalysts to alleviate these problems. This minireview also aims to classify heterogeneous nanostructured electrocatalysts for the CO₂ reduction reaction (CDRR).     

High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts

Nanostructured surfaces have been shown to greatly enhance the activity and selectivity of many different catalysts. Here we report a nanostructured copper surface that gives high selectivity for ethylene formation from electrocatalytic CO₂ reduction. The nanostructured copper is easily formed in situ during the CO₂ reduction reaction, and scanning electron microscopy (SEM) shows the surface to be dominated by cubic structures. Using online electrochemical mass spectrometry (OLEMS), the onset potentials and relative selectivity toward the volatile products (ethylene and methane) were measured for several different copper surfaces and single crystals, relating the cubic shape of the copper surface to the greatly enhanced ethylene selectivity. The ability of the cubic nanostructure to so strongly favor multicarbon product formation from CO₂ reduction, and in particular ethylene over methane, is unique to this surface and is an important step toward developing a catalyst that has exclusive selectivity for multicarbon products.     

Recent advances in single atom catalysts for the electrochemical carbon dioxide reduction reaction

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO₂RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO₂RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C₁ products and formation of C₂₊ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO₂RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO₂RR are raised and possible solutions are provided.

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels.     

Current progress of molybdenum carbide-based materials for electrocatalysis: potential electrocatalysts with diverse applications

Electrocatalysts are the cores of many electrochemical reactions including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), and CO₂ reduction reaction (CO₂RR). Recent advances in research have demonstrated the potentials of molybdenum carbide-based catalysts for these reactions arising out of their unique electronic structure and physicochemical properties. In this review, we systematically summarize the recent advances of molybdenum carbide-based catalysts in these electrochemical processes. The corresponding synthesis strategies, structure and electrocatalytic performance of the catalysts are discussed and the relationships of the process-structure-property are highlighted. In addition, the catalytic mechanisms are analyzed based on the structure characterization and theoretical calculations results. Finally, the existing challenges and future perspectives are put forward for further development of molybdenum carbide-based catalysts.     

A Water-Soluble Sodium Pectate Complex with Copper as an Electrochemical Catalyst for Carbon Dioxide Reduction

A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO₂ reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO₂ to CH₄ in water. Stability and selectivity of conversion of CO₂ to CH₄ as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO₂ reduction reaction (CO₂RR) proceeds at −1.5 V vs. Ag/AgCl at ~10 mA/cm² current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO₂). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts.     

Positive Valent Metal Sites in Electrochemical CO2 Reduction Reaction

The discovery of high-performance catalysts for the electrochemical CO₂ reduction reaction ( CO₂RR) has faced an enormous challenge for years. The lack of cognition about the surface active structures or centers of catalysts in complex conditions limits the development of advanced catalysts for CO₂RR. Recently, the positive valent metal sites (PVMS) are demonstrated as a kind of potential active sites, which can facilitate carbon dioxide (CO₂) activation and conversation but are always unstable under reduction potentials. Many advanced technologies in theory and experiment have been utilized to understand and develop excellent catalysts with PVMS for CO₂RR. Here, we present an introduction of some typical catalysts with PVMS in CO₂RR and give some understanding of the activity and stability for these related catalysts.     

Selective CO2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring

Production of multicarbon products (C₂₊) from CO₂ electroreduction reaction (CO₂RR) is highly desirable for storing renewable energy and reducing carbon emission. The electrochemical synthesis of CO₂RR catalysts that are highly selective for C₂₊ products via electrolyte‐driven nanostructuring is presented. Nanostructured Cu catalysts synthesized in the presence of specific anions selectively convert CO₂ into ethylene and multicarbon alcohols in aqueous 0.1 m KHCO₃ solution, with the iodine‐modified catalyst displaying the highest Faradaic efficiency of 80 % and a partial geometric current density of ca. 31.2 mA cm^?2 for C₂₊ products at ?0.9 V vs. RHE. Operando X‐ray absorption spectroscopy and quasi in situ X‐ray photoelectron spectroscopy measurements revealed that the high C₂₊ selectivity of these nanostructured Cu catalysts can be attributed to the highly roughened surface morphology induced by the synthesis, presence of subsurface oxygen and Cu⁺ species, and the adsorbed halides.     

Effect of pore diameter and length on electrochemical CO2 reduction reaction at nanoporous gold catalysts

In this work, we employ differential electrochemical mass spectrometry (DEMS) to track the real-time evolution of CO at nanoporous gold (NpAu) catalysts with varying pore parameters (diameter and length) during the electrochemical CO₂ reduction reaction (CO₂RR). We show that due to the increase in the local pH with increasing catalyst roughness, NpAu catalysts suppress the bicarbonate-mediated hydrogen evolution reaction (HER) compared to a flat Au electrode. Additionally, the geometric current density for CO₂RR increases with the roughness of NpAu catalysts, which we attribute to the increased availability of active sites at NpAu catalysts. Together, the enhancement of CO₂RR and the suppression of competing HER results in a drastic increase in the faradaic selectivity for CO₂RR with increasing pore length and decreasing pore diameter, reaching near 100% faradaic efficiency for CO in the most extreme case. Interestingly, unlike the geometric current density, the specific current density for CO₂RR has a more complicated relation with the roughness of the NpAu catalysts. We show that this is due to the presence of ohmic drop effects along the length of the porous channels. These ohmic drop effects render the pores partially electrocatalytically inactive and hence, they play an important role in tuning the CO₂RR activity on nanoporous catalysts.

In this work, we employ differential electrochemical mass spectrometry (DEMS) to track the real-time evolution of CO at nanoporous gold (NpAu) catalysts with varying pore parameters (diameter and length) during the electrochemical CO₂ reduction reaction (CO₂RR).     

Cu/CdCO3 catalysts for efficient electrochemical CO2 reduction over the wide potential window

High efficiency and low-cost catalyst-driven electrocatalytic CO₂ reduction to CO production are of great significance for energy storage and development. The severe competitive hydrogen evolution reaction occurs at large negative potential window limits the achievement of the target product from CO₂ at high efficiency. Here, we successfully prepared Cu_x/CdCO₃ composite catalyst rich in interfaces, in which achieved high CO Faraday efficiency exceeded 90% in a wide potential window of 700 mV and highest value up to 97.9% at −0.90 V vs. RHE. The excellent performance can be ascribed to the positive contribution of Cu_x/CdCO₃, which maintains a suitable high local pH value during electrochemical reduction, thus inhibiting the competitive hydrogen evolution reaction. Moreover, the compact structure between Cu and CdCO₃ ensures fast electron transfer both inside catalysts and interface, thus speeding up the reaction kinetics of CO₂ to CO conversion. Theoretically calculations further prove that the combination of Cu and CdCO₃ provides the well-defined electronic structure for intermediates adsorption, significantly reducing the reaction barrier for the formation of CO. This work provides new insights into the design of efficient electrochemical CO₂ reduction catalysts for inhibiting hydrogen evolution by adjusting the local pH effect.     

A Dendritic Nanostructured Copper Oxide Electrocatalyst for the Oxygen Evolution Reaction

To use water as the source of electrons for proton or CO₂ reduction within electrocatalytic devices, catalysts are required for facilitating the proton‐coupled multi‐electron oxygen evolution reaction (OER, 2 H₂O→O₂+4 H⁺+4 e⁻). These catalysts, ideally based on cheap and earth abundant metals, have to display high activity at low overpotential and good stability and selectivity. While numerous examples of Co, Mn, and Ni catalysts were recently reported for water oxidation, only few examples were reported using copper, despite promising efficiencies. A rationally designed nanostructured copper/copper oxide electrocatalyst for OER is presented. This material derives from conductive copper foam passivated by a copper oxide layer and further nanostructured by electrodeposition of CuO nanoparticles. The generated electrodes are highly efficient for catalyzing selective water oxidation to dioxygen with an overpotential of 290 mV at 10 mA cm⁻² in 1 m NaOH solution.     

Electrochemical Reduction of Carbon Dioxide to Ethanol: An Approach to Transforming Greenhouse Gas to Fuel Source

Converting carbon dioxide (CO₂) into high-value fuels or chemicals is considered as a promising way to utilize CO₂ and alleviate the excessive greenhouse gas emission. Among multiple catalysis approaches, electrochemical reduction of CO₂ to ethanol has an important prospect due to the high energy density and widely applications of ethanol. In recent years, many electrocatalysts for CO₂ reduce reaction (CO₂RR) have shown promising catalytic activity for ethanol production. In this review, we will introduce the recent progress in this field. The basic principles and electrochemical performances of CO₂RR are reviewed at first. Then, several categories of active electrocatalysts for CO₂RR to ethanol are summarized, including the discussion of reaction mechanism and catalytic sites. Finally, several possible strategies are proposed, providing guidance for future design and preparation of high-performance catalysts.     

Enhancing CO2 Electroreduction to Methane with a Cobalt Phthalocyanine and Zinc–Nitrogen–Carbon Tandem Catalyst

Developing copper-free catalysts for CO₂ conversion into hydrocarbons and oxygenates is highly desirable for electrochemical CO₂ reduction reaction (CO₂RR). Herein, we report a cobalt phthalocyanine (CoPc) and zinc–nitrogen–carbon (Zn-N-C) tandem catalyst for CO₂RR to CH₄. This tandem catalyst shows a more than 100 times enhancement of the CH₄/CO production rate ratio compared with CoPc or Zn-N-C alone. Density functional theory (DFT) calculations and electrochemical CO reduction reaction results suggest that CO₂ is first reduced into CO over CoPc and then CO diffuses onto Zn-N-C for further conversion into CH₄ over Zn-N₄ site, decoupling complicated CO₂RR pathway on single active site into a two-step tandem reaction. Moreover, mechanistic analysis indicates that CoPc not only generates CO but also enhances the availability of *H over adjacent N sites in Zn-N₄, which is the key to achieve the high CH₄ production rate and understand the intriguing electrocatalytic behavior which is distinctive to copper-based tandem catalysts.     

Development in the green synthesis of cyclic carbonate from carbon dioxide using ionic liquids

This brief review presents the recent development in the synthesis of cyclic carbonate from carbon dioxide (CO₂) using ionic liquids as catalyst and/or reaction medium. The synthesis of cyclic carbonate includes three aspects: catalytic reaction of CO₂ and epoxide, electrochemical reaction of CO₂ and epoxide, and oxidative carboxylation of olefin. Some ionic liquids are suitable catalysts and/or solvents to the CO₂ fixation to produce cyclic carbonate. The activity of ionic liquid is greatly enhanced by the addition of Lewis acidic compounds of metal halides or metal complexes that have no or low activity by themselves. Using ionic liquids for the electrochemical synthesis of the cyclic carbonate can avoid harmful organic solvents, supporting electrolytes and catalysts, which are necessary for conventional electrochemical reaction systems. Although the ionic liquid is better for the oxidative carboxylation of olefin than the ordinary catalysts reported previously, this reaction system is at a preliminary stage. Using the ionic liquids, the synthesis process will become greener and simpler because of easy product separation and catalyst recycling and unnecessary use of volatile and harmful organic solvents.     

The atomic-level regulation of single-atom site catalysts for the electrochemical CO2 reduction reaction

The electrochemical CO₂ reduction reaction (CO₂RR) is viewed as a promising way to remove the greenhouse gas CO₂ from the atmosphere and convert it into useful industrial products such as methane, methanol, formate, ethanol, and so forth. Single-atom site catalysts (SACs) featuring maximum theoretical atom utilization and a unique electronic structure and coordination environment have emerged as promising candidates for use in the CO₂RR. The electronic properties and atomic structures of the central metal sites in SACs will be changed significantly once the types or coordination environments of the central metal sites are altered, which appears to provide new routes for engineering SACs for CO₂ electrocatalysis. Therefore, it is of great importance to discuss the structural regulation of SACs at the atomic level and their influence on CO₂RR activity and selectivity. Despite substantial efforts being made to fabricate various SACs, the principles of regulating the intrinsic electrocatalytic performances of the single-atom sites still needs to be sufficiently emphasized. In this perspective article, we present the latest progress relating to the synthesis and catalytic performance of SACs for the electrochemical CO₂RR. We summarize the atomic-level regulation of SACs for the electrochemical CO₂RR from five aspects: the regulation of the central metal atoms, the coordination environments, the interface of single metal complex sites, multi-atom active sites, and other ingenious strategies to improve the performance of SACs. We highlight synthesis strategies and structural design approaches for SACs with unique geometric structures and discuss how the structure affects the catalytic properties.

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising way to remove CO₂ and convert it into useful industrial products. Single-atom site catalysts provide opportunities to regulate the active sites of CO₂RR catalysts at the atomic level.     

Electrochemical and FTIR spectroscopic study of CO2 reduction at a nanostructured Cu/reduced graphene oxide thin film

Here we report a facile approach to synthesize a novel nanostructured thin film comprising Cu nanoparticles (NPs) and reduced graphene oxide (rGO) on a glassy carbon electrode (GCE) via the direct electrochemical reduction of a mixture of cupper and graphene oxide (GO) precursors. The effect of the applied potential on the electrochemical reduction of CO₂ was investigated using linear sweep voltammetric (LSV) and chronoamperometric (CA) techniques. Carbon monoxide and formate were found as the main products based on our GC and HPLC analysis. The electrochemical reduction of CO₂ at the Cu/rGO thin film was further studied using in situ ATR-FTIR spectroscopy to identify the liquid product formed at different applied cathodic potentials. Our experimental measurements have shown that the nanostructured Cu/rGO thin film exhibits an excellent stability and superb catalytic activity for the electrochemical reduction of CO₂ in an aqueous solution with a high current efficiency of 69.4% at − 0.6 V vs. RHE, promising for the efficient electrochemical conversion of CO₂ to valuable products.     

Chelating N‐Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO₂ reduction. Palladium functionalized with a chelating tris‐N‐heterocyclic carbene (NHC) ligand (Pd‐timtmb^Me) exhibits a 32‐fold increase in activity for electrochemical reduction of CO₂ to C1 products with high Faradaic efficiency (FE_C1=86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC‐ligated Pd electrode (Pd‐mimtmb^Me). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular‐materials interfaces enabled by surface organometallic chemistry.     

Transition Metal Nitrides as Promising Catalyst Supports for Tuning CO/H2 Syngas Production from Electrochemical CO2 Reduction

The electrochemical carbon dioxide reduction reaction (CO₂RR) to produce synthesis gas (syngas) with tunable CO/H₂ ratios has been studied by supporting Pd catalysts on transition metal nitride (TMN) substrates. Combining experimental measurements and density functional theory (DFT) calculations, Pd‐modified niobium nitride (Pd/NbN) is found to generate much higher CO and H₂ partial current densities and greater CO Faradaic efficiency than Pd‐modified vanadium nitride (Pd/VN) and commercial Pd/C catalysts. In‐situ X‐ray diffraction identifies the formation of PdH in Pd/NbN and Pd/C under CO₂RR conditions, whereas the Pd in Pd/VN is not fully transformed into the active PdH phase. DFT calculations show that the stabilized *HOCO and weakened *CO intermediates on PdH/NbN are critical to achieving higher CO₂RR activity. This work suggests that NbN is a promising substrate to modify Pd, resulting in an enhanced electrochemical conversion of CO₂ to syngas with a potential reduction in precious metal loading.     

Bioelectrocatalytic CO2 Reduction by Mo-Dependent Formylmethanofuran Dehydrogenase

Massive efforts are invested in developing innovative CO₂-sequestration strategies to counter climate change and transform CO₂ into higher-value products. CO₂-capture by reduction is a chemical challenge, and attention is turned toward biological systems that selectively and efficiently catalyse this reaction under mild conditions and in aqueous solvents. While a few reports have evaluated the effectiveness of isolated bacterial formate dehydrogenases as catalysts for the reversible electrochemical reduction of CO₂, it is imperative to explore other enzymes among the natural reservoir of potential models that might exhibit higher turnover rates or preferential directionality for the reductive reaction. Here, we present electroenzymatic catalysis of formylmethanofuran dehydrogenase, a CO₂-reducing-and-fixing biomachinery isolated from a thermophilic methanogen, which was deposited on a graphite rod electrode to enable direct electron transfer for electroenzymatic CO₂ reduction. The gas is reduced with a high Faradaic efficiency (109±1 %), where a low affinity for formate prevents its electrochemical reoxidation and favours formate accumulation. These properties make the enzyme an excellent tool for electroenzymatic CO₂-fixation and inspiration for protein engineering that would be beneficial for biotechnological purposes to convert the greenhouse gas into stable formate that can subsequently be safely stored, transported, and used for power generation without energy loss.     

Redox Replacement of Silver on MOF-Derived Cu/C Nanoparticles on Gas Diffusion Electrodes for Electrocatalytic CO2 Reduction

Bimetallic tandem catalysts have emerged as a promising strategy to locally increase the CO flux during electrochemical CO₂ reduction, so as to maximize the rate of conversion to C−C-coupled products. Considering this, a novel Cu/C−Ag nanostructured catalyst has been prepared by a redox replacement process, in which the ratio of the two metals can be tuned by the replacement time. An optimum Cu/Ag composition with similarly sized particles showed the highest CO₂ conversion to C₂₊ products compared to non-Ag-modified gas-diffusion electrodes. Gas chromatography and in-situ Raman measurements in a CO₂ gas diffusion cell suggest the formation of top-bound linear adsorbed *CO followed by consumption of CO in the successive cascade steps, as evidenced by the increasingνC−H bands. These findings suggest that two mechanisms operate simultaneously towards the production of HCO₂H and C−C-coupled products on the Cu/Ag bimetallic surface.     

Electrochemical reduction of CO2 in water-acetonitrile mixtures on nanostructured Cu electrode

This communication studies the CO₂ reduction reaction in H₂O/CH₃CN mixtures on nanostructured copper. It was found that the nanostructured copper electrode presents a well-defined voltammogram in acetonitrile, where it can be seen three signals related to adsorbed or surface attached (thin films) species. Also, it was found that the current density of CO₂ reduction in mixtures H₂O/CH₃CN on nanostructured copper electrodes with a mole fraction around 0.25 is higher than those observed with mole fractions lower than 0.15 or higher than 0.35. Finally, nanostructured Cu electrodes show higher catalytic activity towards the CO₂ reduction than copper electrode.