CO2 Reduction Reaction Research Articles

Parameter Dependency of Electrochemical Reduction of CO2 in Acetonitrile – A Data Driven Approach

The electrochemical CO2 reduction reaction (CO2RR) is a promising technology for the utilization of captured CO2. Though systems using aqueous electrolytes is the state‐of‐the‐art, CO2RR in aprotic solvents are a promising alternative that can avoid the parallel hydrogen evolution reaction (HER). While system parameters, such as electrolyte composition, electrode material, and applied potential are known to influence the reaction mechanism, there is a lack of intuitive understanding as to how. We show that by using multivariate data analysis on a large dataset collected from the literature, namely random forest modelling, the most important system parameters can be isolated for each possible product. We find that water content, current density, and applied potential are powerful determinants in the reaction pathway, and therefore in the Faradaic efficiency of CO2RR products.

Ionomer and Membrane Designs for Low-temperature CO2 and CO Electrolysis.

Low-temperature electroreduction of CO2 and CO (CO(2)RR) into valuable chemicals and fuels offers a promising pathway to reduce greenhouse gas emissions and achieve carbon neutrality. Today's low-temperature CO(2)RR technology relies on the use of ionomers, polymers with ionized groups, primarily as catalyst layer (CL) additives. In the meantime, ionomers can assemble into ion-exchange membranes (IEMs), serving as important components of electrolyzers. According to the ion-exchange functions, ionomer additives are classified as cation-exchange ionomers (CEIs) and anion-exchange ionomers (AEIs); similarly, IEMs are divided into cation-exchange membranes (CEMs) and anion-exchange membranes (AEMs), as well as the multilayer polymer electrolytes (MPEs). Recent studies show that ionomer additives can regulate the catalytic microenvironment and thereby enhance performance towards desired products. This Review discusses the roles of ionomer additives and IEMs in CO2 and CO reduction reactions, highlighting the latest mechanistic insights and performance advances. It outlines challenges in designing ionomer additives and IEMs to improve product selectivity, energy efficiency (EE), and operational lifetime of CO(2)RR electrolyzers, while also providing perspectives on future research directions. The aim is to connect the current status of ionomer and membrane development with performance metrics analysis, offering insights for the advancement of commercially relevant low-temperature CO(2)RR electrolyzers.

Recent advances and future perspectives of metal-organic frameworks as efficient electrocatalysts for CO2 reduction

AbstractThe conversion of carbon dioxide (CO2) to the reduced chemical compounds offers substantial environmental benefits through minimizing the emission of greenhouse gas and fostering sustainable practices. Recently, the unique properties of metal-organic frameworks (MOFs) make them attractive candidates for electrocatalytic CO2 reduction reaction (CO2RR), providing many opportunities to develop efficient, selective, and environmentally sustainable processes for mitigating CO2 emissions and utilizing CO2 as a valuable raw material for the synthesis of fuels and chemicals. Here, the recent advances in MOFs as efficient catalysts for electrocatalytic CO2RR are summarized. The detailed characteristics, electrocatalytic mechanisms, and practical approaches for improving the electrocatalytic efficiency, selectivity, and durability of MOFs under realistic reaction conditions are also clarified. Furthermore, the outlooks on the prospects of MOF-based electrocatalysts in CO2RR are provided.

TM and P dual sites on polymeric carbon nitride enable highly selective CO reduction to C2 products with low potentials: A theoretical perspective.

The CO reduction reaction (CORR) for the production of high-value-added multi-carbon (C2+) products is currently being actively investigated, where searching for high-efficiency catalysts with moderate CO intermediate binding strength and low kinetic barrier for C-C coupling poses a significant challenge. In this study, we employed density functional theory computations to design four synergistic coupling dual sites catalysts for CORR to C2 products, namely, TM-P@melon, by co-doping transition metals (TM = Mn, Fe, Co, and Ni) and phosphorus (P) into the polymeric carbon nitride (i.e., melon-CN). Mn-P@melon and Ni-P@melon exhibit higher selectivity toward C2H5OH and C2H6, respectively, with limiting potentials (C-C coupling kinetic energy barriers) of -0.43V (0.52eV) and -0.17V (0.26eV), respectively. The introduction of TM and P atoms not only narrows the band gap of melon-CN but also favors the coupling of CO and *CHO, providing an active site for C-C coupling, thus facilitating the catalytic reaction. Our work provides rational insights for the design of stable, low-cost, and efficient CORR dual sites catalysts that facilitate the sustainable production of high-value C2 chemicals and fuels.

Precise Synthesis of Dual‐Single‐Atom Electrocatalysts through Pre‐Coordination‐Directed in Situ Confinement for CO2 Reduction

AbstractDual‐single‐atom catalysts (DSACs) are the next paradigm shift in single‐atom catalysts because of the enhanced performance brought about by the synergistic effects between adjacent bimetallic pairs. However, there are few methods for synthesizing DSACs with precise bimetallic structures. Herein, a pre‐coordination strategy is proposed to precisely synthesize a library of DSACs. This strategy ensures the selective and effective coordination of two metals via phthalocyanines with specific coordination sites, such as −F− and −OH−. Subsequently, in situ confinement inhibits the migration of metal pairs during high‐temperature pyrolysis, and obtains the DSACs with precisely constructed metal pairs. Despite changing synthetic parameters, including transition metal centers, metal pairs, and spatial geometry, the products exhibit similar atomic metal pairs dispersion properties, demonstrating the universality of the strategy. The pre‐coordination strategy synthesized DSACs shows significant CO2 reduction reaction performance in both flow‐cell and practical rechargeable Zn‐CO2 batteries. This work not only provides new insights into the precise synthesis of DSACs, but also offers guidelines for the accelerated discovery of efficient catalysts.

Unique Oxygen-Bridged Nickel Atomic Pairs Efficiently Boost Electrochemical Reduction of Carbon Dioxide.

Benefiting from the synergism between adjacent bimetallic atoms, in comparison with single atom catalysts, the dual atom catalysts have displayed great potential in electrocatalytic CO2 reduction reaction (CO2RR). However, the further modulation of the electronic structure of dual atom sites to enhance CO2RR performance still remains a challenge. Herein, an atomically dispersed oxygen-bridged Ni2N6O/NC catalyst with unique Ni-O-Ni sites is successfully synthesized through the microwave pyrolysis of the supported mixture containing the dinuclear nickel phthalocyanine and glucose on N-doped carbon nanosheets. Experiments and density functional theory calculation reveal that the Ni-O-Ni sites can adsorb H+ from the KHCO3 electrolyte to in situ-form the unique Ni-OH-Ni sites without Ni─Ni bonding interaction, which effectively lowers the energy barrier towards the formation of *COOH from CO2. As a result, the Ni2N6OH/NC catalyst exhibits a 99.4% of CO Faradaic efficiency with a 32.4 mA·cm-2 of CO partial current density at -0.7V versus RHE in H-cell, much superior to the Ni2N6/NC with a Ni-Ni bonding interaction prepared by a similar procedure to that for Ni2N6O/NC but replacing microwave pyrolysis by a traditional heating process.

Stability effects of alumina fibers on SnO2/Al2O3 NFs for efficient electrocatalytic performance towards CO2 reduction reaction

Stability effects of alumina fibers on SnO2/Al2O3 NFs for efficient electrocatalytic performance towards CO2 reduction reaction

Ag Atom Induces Microstrain Environment around Cd Sites to Construct Diatomic Sites for Almost 100% CO2-to-CO Electroreduction.

Deeply understanding how local microstrain environment around diatomic sites influences their electronic state and adsorption is crucial for improving electrochemical CO2 reduction (eCO2R) reaction; however, precise engineering of the atomic microstrain environment is challenging. Herein, we fabricate Ag-CdTMT electrocatalysts with AgN2S2-CdN2S2 diatomic sites by anchoring Ag to the nodes of CdTMT (TMT = 2,4,6-trimercaptotriazine anion) coordination polymers. The Ag-CdTMT catalysts achieve approximately 100% Faradaic efficiency for CO reduction with an industrial level current density (∼200 mA cm-2 in H-cell). The embedded Ag atoms induce the formation of Ag-Cd diatomic sites with local microstrain, stretching Cd-N/S bonds, and reinforcing electron localization at Cd sites. The microstrain engineering and adjacent Ag atoms synergistically reduced Cd 4d-C 2p antibonding orbital occupancy for intensifying *COOH adsorption as the rate-determining step. This study provides novel insights into customizing the electronic structure of diatomic sites through strain engineering.

Impact of Side Chains in 1-n-Alkylimidazolium Ionomers on Cu-Catalyzed Electrochemical CO2 Reduction.

This study presents the impact of the side chains in 1-n-alkylimidazolium ionomers with varying side chain lengths (CnH2n+1 where n = 1, 4, 10, 16) on Cu-catalyzed electrochemical CO2 reduction reaction (CO2RR). Longer side chains suppress the H2 and CH4 formation, with the n-hexadecyl ionomer (n = 16) showing the greatest reduction in kinetics by up to 56.5% and 60.0%, respectively. On the other hand, C2H4 production demonstrates optimal Faradaic efficiency with the n-decyl ionomer (n = 10), a substantial increase of 59.9% compared to its methyl analog (n = 1). Through a combination of density functional theory calculations and material characterization, it is revealed that the engineering of the side chains effectively modulates the thermodynamic stability of key intermediates, thus influencing the selectivity of both CO2RR and hydrogen evolution reaction. Moreover, ionomer engineering enables industrially relevant partial current density of -209.5 mA cm-2 and a Faradaic efficiency of 52.4% for C2H4 production at 3.95 V, even with a moderately active Cu catalyst, outperforming previous benchmarks and allowing for further improvement through catalyst engineering. This study underscores the critical role of ionomers in CO2RR, providing insights into their optimal design for sustainable chemicalsynthesis.

Copper Nanoclusters Imparted Metalloporphyrin based Metal-Organic Frameworks for Enhanced CO2 Electroreduction.

Strategies that can introduce catalytic auxiliary into electrocatalysts to boost the performance of electrocatalytic CO2 reduction reaction (CO2RR) are meaningful in exploring hybrid electrocatalytic systems. Here, a series of hybrid elelctrocatalysts (Cu NCs@MOF-545-M, M = Fe, Co and Ni) have been prepared by assembly Cu NCs with MOF-545-M (M = Fe, Co and Ni) and successfully applied in electrocatalytic CO2RR. In the obtained MOF-545-M (M = Fe, Co and Ni), the integration of Cu NCs with MOF-545-M (M = Fe, Co and Ni) can create a hybrid electrocatalytic system that enhances the charge transfer efficiency and electrocatalytic CO2RR activity. Specifically, the optimal Cu NCs@MOF-545-Co achieves high FECO (100%), CO generation rate (10.9 mol m-2 h-1) and energy efficiency (69%), which is superior to Cu NCs and MOF-545-Co, and represented to be one of the best performances to date. This work demonstrates a facile approach to significantly improve the FECO by loading metal nanoclusters into MOFs, providing a valuable reference for future studies on hybridization strategies to enhance the performance of electrocatalysts.

Cu(I)‐Induced ‘Click Reaction’ Involving Coordination and Covalent Assembly of Hybrid Borates for the Electrocatalytic CO2 Reduction

AbstractThe design and synthesis of hybrid borates by the organic ligand modification method are urgent and undeveloped areas of research. It is difficult to directly integrate organoboronic acids within inorganic borate chemistry by adopting the traditional preparation approaches. This work reports a facile synthetic method to synthesize a large family of pyrazole molecule‐protected borates in a rapid and precise manner under mild conditions. A unique cyclic eight‐membered B4O4‐ring has been identified as the cluster core for all these hybrid borates with two different conformations (boat and crown). This strategy can be applied to a system of pyrazolyl molecules to generate such hybrid borates in two independent routes from organoboronic or inorganic boric acids. Furtherly, the mechanism of ‘click reaction’ between boric acid and pyrazole induced by copper ions has been proposed based on the synthetic conditions and the structure of intermediate. Due to the bimetallic Cu sites and the functional surfaces, these materials can be used as electrocatalysts for CO2 reduction reaction and efficiently enhance the selectivity of HCOOH and C2H4. Our strategy can be regarded as a typical template technique for organic molecule‐protected borates.

Integrated “Two‐in‐One” Strategy for High‐Rate Electrocatalytic CO2 Reduction to Formate

AbstractThe electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial‐relevant current densities. Herein, we report a “two‐in‐one” catalyst, defective Bi nanosheets modified by CrOx (Bi−CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi−CrOx exhibits an excellent Faradaic efficiency (≈100 %) in a wide potential range from −0.4 to −0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm−2 at a moderate potential of −0.9 V without iR compensation, the highest value at −0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time.

Asymmetric Charge Distribution in Atomically Precise Metal Nanoclusters for Boosted CO2Reduction Catalysis.

Recently, atomically precise metal nanoclusters (NCs) have been widely applied in CO2 reduction reaction (CO2RR), achieving exciting activity and selectivity and revealing structure-performance correlation. However, at present, the efficiency of CO2RR is still unsatisfactory and cannot meet the requirements of practical applications. One of the main reasons is the difficulty in CO2 activation due to the chemical inertness of CO2. Constructing symmetry-breaking active sites is regarded as an effective strategy to promote CO2 activation by modulating electronic and geometric structure of CO2 molecule. In addition, in the subsequent CO2RR process, asymmetric charge distributed sites can break the charge balance in adjacent adsorbed C1 intermediates and suppress electrostatic repulsion between dipoles, benefiting for C-C coupling to generate C2+ products. Although compared to single atoms, metal nanoparticles, and inorganic materials the research on the construction of asymmetric catalytic sites in metal NCs is in a newly-developing stage, the precision, adjustability and diversity of metal NCs structure provide many possibilities to build asymmetric sites. This review summarizes several strategies of construction asymmetric charge distribution in metal NCs for boosting CO2RR, concludes the mechanism investigation paradigm of NCs-based catalysts, and proposes the challenges and opportunities of NCs catalysis.

Enhanced photoelectrocatalytic CO2 reduction to CO via structure-induced carrier separation in coral-like CuBi2O4-Bi2O3

Significant carrier recombination has severely limited the development of the most potential photoelectrocatalytic CO2 reduction reaction (PEC-CO2 RR). Herein, coral-like CuBi2O4-Bi2O3 photocathodes are prepared using the strategy of the construction of heterojunction to improve the efficiency of carrier separation. As expected, its faradic efficiency of CO (FECO) at the lower potential (0.1 V vs. RHE) is 86.03 %, which is about 1.49 times higher than that of the original CuBi2O4 film. The increased catalytic activity of CuBi2O4-Bi2O3 can be attributed to the high surface area of the distinctive coral-like structure of Bi2O3, which enhances light absorption efficiency. Additionally, the higher degree of band bending in CuBi2O4-Bi2O3 and the built-in electric field can speed up the transport rate of electrons, slow down the recombination of photogenerated electrons with holes and extend the lifetime of photogenerated electrons, allowing electrons to continuously participate in the reaction. This study proposes a novel strategy to optimize the efficiency of photoelectrocatalytic CO2 reduction by CuBi2O4-based photocathodes.

Electrochemical Formation of C2+ Products Steered by Bridge-Bonded *CO Confined by *OH Domains.

During the electrochemical CO2 reduction reaction (eCO2RR) on copper catalysts, linear-bonded CO (*COL) is commonly regarded as the key intermediate for the CO-CO coupling step, which leads to the formation of multicarbon products. In this work, we unveil the significant role of bridge-bonded *CO (*COB) as an active species. By combining in situ Raman spectroscopy, gas and liquid chromatography, and density functional theory (DFT) simulations, we show that adsorbed *OH domains displace *COL to *COB. The electroreduction of a 12CO+13CO2 cofeed demonstrates that *COB distinctly favors the production of acetate and 1-propanol, while *COL favors ethylene and ethanol formation. This work enhances our understanding of the mechanistic intricacies of eCO(2)RR and suggests new directions for designing operational conditions by modifying the competitive adsorption of surface species, thereby steering the reaction toward specific multicarbon products.

In Situ Exsolved CuZn Alloy Electrocatalysts for CO2 Conversion to Tunable Syngas Production

AbstractAlloying is considered as a promising method for syngas (H2 and CO mixture gas) generation. However, it is challenging to elucidate the relationship between the ratios of syngas and alloy components for CO2 reduction reaction. Herein, through tuning the Cu/Zn ratio on CuZn alloy, the H2/CO ratios in CuZn‐2 (Cu/Zn = 0.77) can be tuned in a noticeable range between 0.8 and 5.8 at −0.88 to −1.28 V versus RHE, and a durable stability of 12 h. The CuZn‐2 displays better performance and enhanced dynamics than other samples. Electrochemical impedance spectroscopies and Tafel results reveal that CuZn‐2 behaves kinetically optimized performance. Density functional theory calculations results reveal that CuZn alloy exhibits middle desorption intensity of *H for HER compared with pure Zn and Cu. CuZn alloy effectively decreases the energy barrier of CO2 molecules activated to *COOH relative to Zn, and also the alloy renders it easier for *CO desorb to generate CO for Cu. In situ Fourier transform infrared spectroscopies also observe a significant intensity of *CO on CuZn‐2. This work demonstrates that alloying Cu and Zn can create active sites, in which Cu acts as an auxiliary active site further facilitating *CO generation.

Advances and Challenges of Carbon‐Free Gas‐Diffusion Electrodes (GDEs) for Electrochemical CO2 Reduction

AbstractElectrochemical CO2 reduction reaction (CO2RR) coupled with renewable electricity holds promises for efficient mitigation of carbon emission impacts on the environment and turning CO2 into valuable chemicals. One important task in CO2RR development is the design and fabrication of efficient electrodes for stable operation in the long term. Gas‐diffusion electrodes (GDEs) have been employed to continuously feed CO2 to the electrolyzers. Despite significant advances in GDE design and tailoring GDE properties, the present GDEs often suffer from the critical issue of flooding due to the electrowetting of carbon‐based substrates, which hinders the transition to industrial application. To address flooding, GDEs with intrinsically hydrophobic polymeric substrates have been recently fabricated and have shown promising performances. Herein, the advances and challenges associated with carbon‐free GDEs are reviewed for CO2RR. This review first briefly outlines GDE and electrolyzers basics. Through critical discussion around the shortcomings of conventional carbon‐based GDEs, the most recent efforts to resolve flooding are summarized. Subsequently, the advances, advantages, and challenges of carbon‐free GDEs are elaborated. Finally, priorities for future studies are suggested, with the aim to support the advancement and scale‐up of carbon‐free GDEs and extend them to other electrochemical systems where gas and the electrolyte are in contact.

Regulatory Mechanisms and Applications of Rare Earth Elements‐Based Electrocatalysts†

Comprehensive SummaryAmidst the pressing environmental challenges posed by the prevalent reliance on fossil fuels, it becomes imperative to seek sustainable alternatives and prioritize energy efficiency. Electrocatalysis, which is renowned for its high efficiency and environmental friendliness, has garnered significant attention. Rare earth elements (REEs), distinguished by their unique electronic and orbital structures, play a crucial role in electrocatalysis. The strategic integration of REEs into catalysts allows for the fine‐tuning of atomic structures, which in turn, significantly boosts catalytic performance. Despite substantial advancements in rare earth‐based materials for electrocatalysis, a comprehensive overview of the regulatory mechanisms involving REEs is lacking. In this mini‐review, we systematically explore the regulatory mechanisms of REEs within electrocatalysts and their pivotal roles in essential electrocatalytic processes such as the CO2 reduction reaction, oxygen reduction reaction, and hydrogen evolution reaction. We commence with an elucidation of REEs, proceed to delineate their regulatory impacts on electrocatalysts and delve into their applications in key electroreduction reactions. We conclude with discussions on current limitations and prospects for further advancements in this burgeoning field of research. Key Scientists

Efficient CO2 Reduction Reaction on Cu-Decorated Biphenylene.

Developing efficient electrocatalysts for CO2 reduction into value-added products is crucial for a green economy. Inspired by the recent experimental synthesis of biphenylene (BPH) and the excellent catalytic activity of copper dispersed on two-dimensional (2D) materials, we chose to systematically investigate the pristine, defective, and Cu-decorated BPH for the electrocatalytic CO2 reduction to value-added hydrocarbons. It is observed that the CO2 molecules bind weakly to the pristine BPH, indicating their chemical inertness. Carbon single-vacancy defects facilitate CO2 adsorption with a strong binding energy (Eb) of -3.23 eV, detrimental to the CO2 reduction reaction (CRR) mechanism. We have further investigated the binding energy and kinetic stability of Cu-decorated BPH as a single-atom-catalyst (SAC). The molecular dynamics simulations confirm the kinetic stability, revealing that the Cu-atom avoids agglomeration under low metal dispersal conditions. The CO2 molecule gets adsorbed horizontally on the Cu-BPH surface with a ΔEb of -0.52 eV. The CRR mechanism is investigated using two pathways beginning with two different initial states, formate (*OCOH) and carboxylic (*COOH). The formate pathway confirms the conversion of *OCOH to *HCOOH with the rate-limiting potential (UL) of 0.39 eV for the production of HCOOH, while for the carboxylic pathway, the conversion of *COH to *CHOH has a UL of 0.32 eV, eventually producing CH3OH. Our findings highlight the role of Cu-BPH as an efficient SAC for CO2 catalytic activity to C1 products, as compared to the state-of-the-art Cu, and holds promise as an electrocatalyst for CRR.

Ni-Metalized Covalent Organic Cage as a Photocatalyst for Selective Photoreduction of CO2 to CO.

Metal complex-based photocatalysts are promising for CO2 reduction. Their catalytic performances greatly rely on the synergy of ligands and metal ions. Here, we demonstrate an assembly of covalent organic cage (COC) and metal ions for photocatalytic CO2 reduction. The coordinated metal serves as catalytically active site for CO2 reduction, while the cage not only chelates the metal site, but also enhances the local concentration of CO2 around metal site, and decreases the key intermediate reaction energy barrier, thereby promoting the CO2 reduction reaction kinetically and thermodynamically. Accordingly, a Ni metalized COC exhibited outstanding photocatalytic performance in CO2-to-CO conversion under visible light irradiation. This study highlights the feasibility and advantage of organic cages for the construction of photocatalysts for artificial photosynthesis.