Electrochemical Reduction Reaction Research Articles

Reconstructing Solvation Structure by Steric Hindrance‐Coordination Push‐Pull of Dipolymer‐H2O‐Zn2+ toward Long‐life Aqueous Zinc‐Metal Batteries

AbstractAqueous zinc‐metal batteries are prospective energy storge devices due to their intrinsically high safety and cost effectiveness. Yet, uneven deposition of zinc ions in electrochemical reduction and side reactions at the anode interface significantly hinder their development and application. Here, we propose a solvation‐interface attenuation strategy enabled by a frustrated tertiary amine amphiphilic dipolymer electrolyte additive. The configuration of superhydrophilic segments with covalently bonded lipophilic spacers enables coupled steric hindrance/coordination, which establishes a balanced push‐pull dynamic of dipolymer‐H2O‐Zn2+. Such interplay reconstructs the solvation structure of Zn2+ and allows the formation of a stable dipolymer‐inorganic hybrid solid electrolyte interface (SEI) layer. This SEI layer effectively shields the zinc‐metal anode from water and anions, significantly reducing side reactions. In addition, the dipolymer adsorbed at the zinc‐metal anode interface regulates the interfacial electrochemical reduction kinetics and ensures uniform zinc deposition. As a result, the Zn−Zn symmetric cells with dipolymer‐containing electrolyte exhibit remarkable cycling stability exceeding 5800 h (242 days). The Zn‐NVO batteries and Zn‐AC hybrid ion supercapacitors also deliver stable cycling for up to 1440 h (60 days) with high‐capacity retention over 80 %. This research demonstrates the potential to facilitate the development and commercialization of zinc‐based energy storage devices.

Oxygen Vacancy-Controlled CuOx/N,Se Co-Doped Porous Carbon via Plasma-Treatment for Enhanced Electro-Reduction of Nitrate to Green Ammonia.

The electrochemical nitrate reduction reaction (NO3RR) is of significance in regards of environmentally friendly issues and green ammonia production. However, relatively low performance with a competitive hydrogen evolution reaction (HER) is a challenge to overcome for the NO3RR. In this study, oxygen vacancy-controlled copper oxide (CuOx) catalysts through a plasma treatment are successfully prepared and supported on high surface area porous carbon that are co-doped with N, Se species for its enhanced electrochemical properties. The oxygen vacancy-increased CuOx catalyst supported on the N,Se co-doped porous carbon (CuOx-H/NSePC) exhibited the highest NO3RR performance with faradaic efficiency (FE) of 87.2% and yield of 7.9mg cm-2h-1 for the ammonia production, representing significant enhancements of FE and ammonia yield as compared to the un-doped or the oxygen vacancy-decreased catalysts. This high performance should be attributed to a significant increase in the catalytic active sites with facilitated energetics from strategies of doping the catalytic materials and weakening the N─O bonding strength for the adsorption of NO3 - ions on the modulated oxygen vacancies. This results show a promise that co-doping of heteroatoms and regulating of oxygen vacancies can be key factors for performance enhancement, suggesting new guidelines for effective catalyst design of NO3RR.

Ethylene Electrosynthesis via Selective CO2 Reduction: Fundamental Considerations, Strategies, and Challenges

AbstractThe electrochemical carbon dioxide reduction reaction (CO2RR) is a promising approach for reducing atmospheric carbon dioxide (CO2) emissions, allowing harmful CO2 to be converted into more valuable carbon‐based products. On one hand, single carbon (C1) products have been obtained with high efficiency and show great promise for industrial CO2 capture. However, multi‐carbon (C2+) products possess high market value and have demonstrated significant promise as potential products for CO2RR. Due to CO2RR's multiple pathways with similar equilibrium potentials, the extended reaction mechanisms necessary to form C2+ products continue to reduce the overall selectivity of CO2‐to‐C2+ electroconversion. Meanwhile, CO2RR as a whole faces many challenges relating to system optimization, owing to an intolerance for low surface pH, systemic stability and utilization issues, and a competing side reaction in the form of the H2 evolution reaction (HER). Ethylene (C2H4) remains incredibly valuable within the chemical industry; however, the current established method for producing ethylene (steam cracking) contributes to the emission of CO2 into the atmosphere. Thus, strategies to significantly increase the efficiency of this technology are essential. This review will discuss the vital factors influencing CO2RR in forming C2H4 products and summarize the recent advancements in ethylene electrosynthesis.

Reconstructing Solvation Structure by Steric Hindrance-Coordination Push-Pull of Dipolymer-H2O-Zn2+ toward Long-life Aqueous Zinc-Metal Batteries.

Aqueous zinc-metal batteries are prospective energy storge devices due to their intrinsically high safety and cost effectiveness. Yet, uneven deposition of zinc ions in electrochemical reduction and side reactions at the anode interface significantly hinder their development and application. Here, we propose a solvation-interface attenuation strategy enabled by a frustrated tertiary amine amphiphilic dipolymer electrolyte additive. The configuration of superhydrophilic segments with covalently bonded lipophilic spacers enables coupled steric hindrance/coordination, which establishes a balanced push-pull dynamic of dipolymer-H2O-Zn2+. Such interplay reconstructs the solvation structure of Zn2+ and allows the formation of a stable dipolymer-inorganic hybrid solid electrolyte interface (SEI) layer. This SEI layer effectively shields the zinc-metal anode from water and anions, significantly reducing side reactions. In addition, the dipolymer adsorbed at the zinc-metal anode interface regulates the interfacial electrochemical reduction kinetics and ensures uniform zinc deposition. As a result, the Zn-Zn symmetric cells with dipolymer-containing electrolyte exhibit remarkable cycling stability exceeding 5800 h (242 days). The Zn-NVO batteries and Zn-AC hybrid ion supercapacitors also deliver stable cycling for up to 1440 h (60 days) with high-capacity retention over 80%. This research demonstrates the potential to facilitate the development and commercialization of zinc-based energy storage devices.

Efficient oxygen reduction to alkaline peroxide at current densities up to 500 mA cm−2 on a gas diffusion electrode with hydrophobic carbon microporous layer: Influence of fluid dynamics and reactor operation on scale-up

The two-electron electrochemical O2 reduction reaction (2e-ORR) on a gas diffusion electrode (GDE) using clean electricity is an attractive process for generating the green oxidant hydrogen peroxide (H2O2). Electrolyte flooding through the porous catalyst and diffusion layers is one of the major factors inhibiting the operational stability and longevity under industrially relevant current densities (>100 mA cm−2). This study reports for the first time that optimizing the two-phase flow and the mode of reactor operation brings about a remarkable improvement in the high current density operation (up to 500 mA cm−2) on a scalable (20 cm2 geometric area) and commercially available Sigracet 39BB GDE with the microporous carbon layer (MPL) acting as the catalyst layer. The interacting effects of current density, gas and liquid flow rates and the flooding threshold limit for the differential liquid/gas pressure were determined. While high peroxide Faradaic efficiency (FE > 95 %) was attained in a gas flow-by mode during short-term experiments, long-term stability was only established when the gas was switched to the flow-through or quasi-flow-through mode of operation. Under the latter conditions, at 500 mA cm−2 operational stability of more than 20 h was demonstrated with a peak FE of 97 % in 1.0 M KOH, at 293 K, 1 atm. It was found that optimizing the reactor operation has a profound effect during scale-up, and developing novel catalytic materials for 2e-ORR to alkaline peroxide is not warranted since a low-cost microporous carbon-based GDE is sufficient for stable and efficient operation.

Interfacial Accumulation and Stability Enhancement Effects Triggered by Built-in Electric Field of SnO2/LaOCl Nanofibers Boost Carbon Dioxide Electroreduction.

Constructing a built-in interfacial electric field (BIEF) is an effective approach to enhance the electrocatalysts performance, but it has been rarely demonstrated for electrochemical carbon dioxide reduction reaction (CO2RR) to date. Herein, for the first time, SnO2/LaOCl nanofibers (NFs) with BIEF is created by electrospinning, exhibiting a high Faradaic efficiency (FE) of 100% C1 product (CO and HCOOH) at -0.9--1.1V versus reversible hydrogen electrode (RHE) and a maximum FEHCOOH of 90.1% at -1.2 VRHE in H-cell, superior to the commercial SnO2 nanoparticles (NPs) and LaOCl NFs. SnO2/LaOCl NFs also exhibit outstanding stability, maintaining negligible activity degradation even after 10h of electrolysis. Moreover, their current density and FEHCOOH are almost 400mAcm-2 at -2.31V and 83.4% in flow-cell. The satisfactory CO2RR performance of SnO2/LaOCl NFs with BIEF can be ascribed to tight interface of coupling SnO2 NPs and LaOCl NFs, which can induce charge redistribution, rich active sites, enhanced CO2 adsorption, as well as optimized Gibbs free energy of *OCHO. The work reveals that the BIEF will trigger interfacial accumulation and stability enhancement effects in promoting CO2RR activity and stability of SnO2-based materials, providing a novel approach to develop stable and efficient CO2RR electrocatalysts.

An Energy-Efficient Integrated System by Coupling Carbon Dioxide Reduction and Methanol Oxidation to Produce the Identical Value-Added Formic Acid

Metal-organic frameworks (MOFs) are considered as promising catalytic materials for electrochemical carbon dioxide reduction (ECR) reactions due to their excellent properties. However, the development of efficient and stable electrocatalysts within a wide potential window remains a great challenge. Herein, the rod-like Sn-MOF is synthesized by a fast and simple solution reaction, which has good performance in converting CO2 to HCOOH. In particular, Sn-MOF reaches a maximum Faradaic efficiency of 86.4% at −1.15 V vs RHE with a current density of 25.2 mA cm−2. It is worth noting that Sn-MOF has excellent long-term stability, maintaining more than 80% of FEHCOOH production within 30 h of continuous electrolysis. Meanwhile, X-ray diffraction and X-ray photoelectron spectroscopy characterization confirm that Sn2+ in Sn-MOF can be reduced to Sn0 in the ECR reaction. The theoretical results show that *COOH intermediate tends to form in the ECR process on Sn-MOF, and it has a high selectivity for the formation of HCOOH. In addition, the two-electrode system driving the co-electrolysis of methanol and CO2 can significantly reduce the voltage by 500 mV at a current density of 20 mA cm−2.

Electrodeposition of NdFeB films in DMI−LiNO3 ionic liquid analogs at room temperature

The feasibility and reaction mechanism of NdFeB film electrodeposition in 1,3-dimethyl-2-imidazolidinone (DMI)−LiNO3 ionic liquid analogs at room temperature were investigated. Cyclic voltammetry indicated that the reduction peak at −1.83 V (vs Ag) was related to the reduction of Fe(II) to Fe, while the reduction peak at −2.01 V (vs Ag) was related to the reduction of B(III) to B. The electrochemical reduction reaction of Fe(II) and B(III) were irreversible processes controlled by diffusion, and the diffusion coefficients of Fe(II) and B(III) at 313 K were 3.03×10−6 and 6.74×10−7 cm2/s, respectively. In addition, XRD analysis suggested that the product obtained by the electrodeposition in DMI−LiNO3−Nd(CF3SO3)3−FeCl2−H3BO3 ionic liquid analogs for 2 h on the Al substrate contained NdFe3B3. SEM and EDS analysis showed that Nd, Fe, and B in the cathode product were uniformly distributed. XPS analysis revealed that the mass fractions of Nd, Fe, and B on the W substrate were 27.44%, 27.90%, and 7.51%, respectively.

Transformation of Bi4Cl2S5 into sub-10 nm Bi2O2CO3 nanowires for electrochemical reduction of CO2

The development of highly efficient catalysts for the selective electrochemical reduction reaction of CO2 (eCO2RR) to high-valued formate remains a challenge in achieving carbon neutrality and renewable energy conversion. In this study, ultrathin Bi4Cl2S5 nanowires, synthesized using different branched-chain thiols as sulfur sources, were reported for the first time as precatalysts for eCO2RR to formate. Systematic material characterization demonstrated that Bi4Cl2S5 can undergo in-situ evolution into Bi2O2CO3 nanowires, serving as the genuine electrocatalyst for eCO2RR. Through the fine-tuning of ligands during the synthesis of Bi4Cl2S5 nanowires, the optimized Bi4Cl2S5-derived Bi2O2CO3 nanowires exhibited a maximum formate Faradaic efficiency (FEformate) of 95.3 % in eCO2RR using a traditional H-cell, surpassing other prepared samples. Furthermore, an FEformate of over 92.9 % was achieved in a wide potential window of 500 mV, and high performance was maintained over 20 h. This outstanding performance is attributed to the high intrinsic activity, accelerated charge transfer, and the large electrochemical active surface area associated with the characteristic sub-10 nm diameter nanowire structure. Moreover, density function theory calculations further revealed that Bi2O2CO3 can reduce the energy barriers for the formation of *OCHO intermediate and bolster formate production. Our work provides a novel synthesis strategy for excellent Bi-based catalysts in electrocatalysis.

Mixed Fe-Mo carbide prepared by a sonochemical synthesis as highly efficient nitrate reduction electrocatalyst

Ammonia, a versatile compound that can be used as a fertilizer, chemical or fuel, has since long been produced through the energy-intensive Haber-Bosch process. Recently, the electrochemical nitrate reduction reaction (NO3RR) using electricity generated from renewable sources has attracted widespread attention. However, the complex reaction pathway of NO3RR leads to the formation of many undesirable by-products. Herein we successfully prepared a mixed (FeMo)2C catalyst with good electrocatalytic NO3RR, having a NH3 yield of 14.66 mg h-1 cm-2 and an FE of 94.35% at low potential -0.3 V vs RHE. DFT calculations show that the presence of Fe in Mo2C lattice changes the reaction mechanism, decreasing the potential barrier to be overcome from 1.36 to 0.89 eV. In addition, mixed Fe-Mo carbide facilitates the adsorption of intermediates and promotes NH3 desorption, facilitating NO3− reduction to NH3. In addition, (FeMo)2C was used as cathode for Zn-NO3 battery to generate electricity, producing ammonia at the same time, with a power density of 3.8 mWcm-2 and an NH3 FE of 88%. This work describes a new synthesis method for mixed metal carbides and provides a promising strategy for NH3 production.

Boosting Electrochemical Ammonia Synthesis via NOx Reduction over Sulfur‐Doped Copper Oxide Nanoneedle Arrays

AbstractThe electrochemical NOx reduction reactions, involving nitrate and nitrite reduction reactions (NO3−RR and NO2−RR), have emerged as promising approaches for both NO3− and NO2− removal, and ammonium (NH3) synthesis under ambient conditions. However, the incorporation and stabilization of sulfur dopants in the catalysts for efficient NOx reduction are rarely explored, leading to an unclear effect of sulfur on the NOx reduction mechanism. Herein, sulfur‐doped Cu2O (S‐Cu2O) nanoneedle arrays via in situ electrochemical treatment are synthesized. The S‐Cu2O catalyst possesses excellent durability and selectivity for NH3 over a wide range of potentials in NO3−RR, attaining a maximum NH3 Faradaic efficiency of 94% at −0.6 VRHE and a maximum NH3 yield as high as 1.06 mmol h−1 cm−2. In NO3−RR, the sulfur dopant can accelerate the step from NO2− to NH3, contributing superior performance in NO2−RR and assembled Zn−NO2− battery device. Density functional theory (DFT) calculations reveal that the presence of sulfur can enhance the initial step of *NO3 adsorption, lower the reaction barriers for the formation of *NHO intermediate, and activate the H2O dissociation process. The work sheds light on the role of sulfur in enhancing electrocatalytic performance and provides a unique perspective for understanding the NOx reduction mechanism.

Design and synthesis of heteroleptic Ni(II) dipyrrin complexes for electrochemical proton reduction reactions: Cyclic voltammetric and theoretical studies

The effect of nuclearity on electrochemical hydrogen generation using new heteroleptic Ni(II) complexes containing redox-active dipyrrin and dithiocarbamate ligands has been described. Complexes 1–2 have been meticulously characterized by spectroscopic studies (ESI-MS, IR, 1H, 13C NMR, UV–vis) and their structures unambiguously confirmed by X-ray single crystal analyses. Electrocatalytic properties of the complexes toward hydrogen evolution reaction have been investigated by cyclic voltammetric studies in an organic medium in the presence of acetic acid as a weak proton source. Notably, complexes 1 and 2 produce H2 via doubly reduced Ni(II) species i.e. Ni(0) in the presence of acetic acid. Further, these complexes exhibited significant electrocatalytic activity (TOF: 264 (1) and 650 s−1 (2). Controlled potential electrolysis established a minimum Faradaic efficiency of 92 (1) and 96 % (2). Complex 2 exhibited higher turnover frequency relative to 1, while 1 showed lower overpotential (0.35 V) in comparison to 2 (0.45 V). The stability of the complexes and the amount of produced H2 has been investigated by bulk electrolysis study. A tentative mechanism (ECEC; E, electrons and C, chemical steps) and involved intermediate species for the proton reduction reaction for 1 has been established by theoretical studies.

Unveiling the facet-dependent activity of Cu2O for enhanced selective electroreduction of nitric oxide to ammonia and Zn-NO batteries

The conversion of harmful industrial-emitted nitric oxide from emission into valuable NH3 through NO electrochemical reduction reaction (NORR) is a green and sustainable route, which can enable the nitrogen cycle. However, exploring efficient catalyst and unveiling relevant intrinsic mechanism remains a big challenge for improving the efficiency. Herein, we delve into the facet-dependent activity of Cu2O nanocrystal, unveiling for the superior performance of oxygen-vacancy-anchored Cu2O (111) with an unprecedented NH3 yield of 273.5 μmol h−1 cm−2 and a Faradaic efficiency of 96.9% at −0.4 V vs RHE, which is significantly higher than that of Cu2O (100) and Cu2O (100)&(111). Cu2O (111) with abundant oxygen vacancies and hydroxyl groups facilitated the adsorption of NO and suppressed the hydrogen evolution reaction (HER), insights supported by theoretical calculations and in-situ attenuated total reflectance-surface-enhanced IR absorption spectroscopy (ATR-SEIRAS). Further, leveraging Cu2O (111) as the cathode, a proof-of-concept Zn-NO battery delivered superior performance with a power density of 4.62 mW cm−2 and an NH3 yield of 308.0 μg h−1 cm−2. This work not only elucidates the facet-dependent catalytic behaviors but also sets a new benchmark for NH3 synthesis and Zn-NO battery development, presenting a significant advancement in the sustainable and efficient conversion of nitric oxide.

Semimetallic state transition in Two-Dimensional carbon nitride covalent networks and enhanced electrocatalytic activity for nitrate to ammonia conversion

Single-atom catalysts (SACs), due to their maximum atomic utilization rate, show tremendous potential for application in the electrocatalytic synthesis of ammonia from nitrate. Yet, the development of superior supports that preserve the high selectivity, activity, and stability of SACs remains an imperative challenge. In this work, based on first-principles calculations and tight-binding (TB) model analysis, a new two-dimensional (2D) carbon nitride monolayer, C7N6, is proposed. The C7N6 structure exhibits a strong covalent network, with dynamical, thermal, and mechanical stability. Surprisingly, the structural transition from C9N4 to C7N6 corresponds to a semimetallic state transition. Further symmetry analysis unveils that the Dirac states in C7N6 are protected by space–time inversion symmetry, and the physical origin of the Dirac cone was confirmed using the TB model. Additionally, a non-zero Z2 invariant and significant topological edge states demonstrate its topologically nontrivial nature. Considering the excellent structural and topological properties of C7N6, a three-step screening strategy is designed to identify eligible SACs for electrochemical nitrate reduction reaction (NO3RR), and Ti@C7N6 is identified as possessing the best activity, with the last proton-electron coupling step *NH2→*NH3 being the potential-determining step (PDS), for which the limiting potential is 0.48 V. Moreover, a free energy diagram shows that the *NOH reaction pathway is energetically preferred on Ti@C7N6, and ab initio molecular dynamics (AIMD) calculations at 500 K confirm its good thermal stability. Our study not only provides excellent CN-based support material but also offers theoretical guidance for constructing highly active and selective SACs for nitrate reduction.

Cu-based nano-material catalysts for electrochemical carbon dioxide reduction reaction (CO2RR)

With the emergence of the global energy crisis and global climate change, renewable energy systems, such as fuel cells that turn off energetic oxygen and carbon cycles, are becoming increasingly important. Carbon dioxide reduction reaction (CO_2 RR) is an important electrocatalytic process on the gas diffusion electrode of CO_2 electrolyzer, which has been paid more and more attention by researchers. The problems of high cost, low efficiency, weak selectivity and stability of the carbon dioxide reduction reaction (CO_2 RR) also continue to be solved. Catalysts are considered a viable way to solve these problems. The Cu-based nanomaterial catalyst has been proven to have a good positive effect on the reaction. In this paper, the current research results of Cu-based nanomaterials on CO_2 RR were reviewed, and the catalytic effects of several different Cu-based nanomaterials on CO_2 RR reactions were compared. This paper collected the researches on the catalytic effect of copper-based nanomaterials on carbon dioxide reduction reactions in the past ten years, and found that most copper-based nanomaterials can improve the efficiency of the reactions and show good selectivity. The aim of this paper is to provide a possible catalytic direction for the improvement of carbon dioxide reduction reactions in industry

Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate.

Electrochemical carbon dioxide/carbon monoxide reduction reaction offers a promising route to synthesize fuels and value-added chemicals, unfortunately their activities and selectivities remain unsatisfactory. Here, we present a general surface molecular tuning strategy by modifying Cu2O with a molecular pyridine-derivative. The surface modified Cu2O nanocubes by 4-mercaptopyridine display a high Faradaic efficiency of greater than 60% in electrochemical carbon monoxide reduction reaction to acetate with a current density as large as 380 mA/cm2 in a liquid electrolyte flow cell. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveals stronger *CO signal with bridge configuration and stronger *OCCHO signal over modified Cu2O nanocubes by 4-mercaptopyridine than unmodified Cu2O nanocubes during electrochemical CO reduction. Density function theory calculations disclose that local molecular tuning can effectively regulate the electronic structure of copper catalyst, enhancing *CO and *CHO intermediates adsorption by the stabilization effect through hydrogen bonding, which can greatly promote asymmetric *CO-*CHO coupling in electrochemical carbon monoxide reduction reaction.

Plasma induced grain boundaries to boost electrochemical reduction of CO2 to formate

Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction (eCO2RR) to formate product. However, achieving high activity and selectivity towards formate and ensuring long-term stability remains challenging. This work reports the oxygen plasma inducing strategy to construct the abundant grain boundaries of Bi/BiOx on ultrathin two-dimensional Bi nanosheets. The oxygen plasma-treated Bi nanosheet (OP-Bi) exhibits over 90% Faradaic efficiency (FE) for formate at a wide potential range from −0.5 to −1.1 V, and maintains a great stability catalytic performance without significant decay over 30 h in flow cell. Moreover, membrane electrode assembly (MEA) device with OP-Bi as catalyst sustains the robust current density of 100 mA cm−2 over 50 h, maintaining a formate FE above 90%. In addition, rechargeable Zn-CO2 battery presents the peak power density of 1.22 mW cm−2 with OP-Bi as bifunctional catalyst. The mechanism experiments demonstrate that the high-density grain boundaries of OP-Bi provide more exposed active sites, faster electron transfer capacity, and the stronger intrinsic activity of Bi atoms. In situ spectroscopy and theoretical calculations further elucidate that the unsaturated Bi coordination atoms between the grain boundaries can effectively activate CO2 molecules through elongating the C–O bond, and reducing the formation energy barrier of the key intermediate (*OCOH), thereby enhancing the catalytic performance of eCO2RR to formate product.

Detection of electrocatalytical and -chemical processes by means of in situ flow NMR spectroscopy

In situ studies of electrochemical processes using NMR offer valuable information on reaction mechanisms, kinetics, and species identification, making it a powerful tool in electrochemistry research. In this study, we present the design of an in situ redox-flow NMR cell that allows for a continuous flow of liquid (electrolyte) or gas, application of electrical voltage, and recording of NMR signals. The utility of this setup is demonstrated through two case studies: electrochemical copper deposition on a gold electrode and the electrochemical conversion of carbon dioxide into hydrocarbon products. Specifically, the presence of multicarbon products containing C–C bonds generated during the electrochemical reduction reaction is confirmed in the 2H NMR spectra in the latter example. These findings highlight the ability of the in situ redox-flow NMR cell to directly monitor reaction intermediates and products, thereby enabling the elucidation of reaction mechanisms for the efficient and selective production of valuable hydrocarbon products through the conversion of CO2 into value-added chemicals. In contrast to other reported in situ NMR cells, the presented cell is suitable for multiple uses, and allows detecting NMR signals not only from exhaust products but also from those formed on the catalyst surface.

Effect of loading and pyrolysis of carbon-supported cobalt phthalocyanine on the electrocatalytic reduction of CO2

Understanding the structure-activity relationship of materials that are active for the CO2 electrochemical reduction reaction (CO2ERR) is crucial for developing stable, high-performance catalysts. In this research, it is first shown that ball-milling is a highly efficient way to disperse cobalt phthalocyanine (CoPC) onto carbon black without influencing the CO2 electroreduction performance of the resulting materials. Then, the link between the loadings of the CoPC precursor on the carbon support and the CO2ERR activity of the pyrolyzed materials is demonstrated. With CO current efficiencies higher than 45% and CO current densities as high as -20 mA cm−2 at -0.77 V vs. RHE, the materials with CoPC loadings of 7.9 wt% and higher were still surprisingly active after pyrolysis at 800 and 900 °C. On the other hand, the CO2ERR activity of the materials containing less than 6.1 wt% CoPC was drastically reduced after pyrolysis at these temperatures, with CO current efficiencies lower than 10 %. X-ray powder diffraction revealed that only the materials containing crystalline CoPC before pyrolysis showed good CO2ERR activity after pyrolysis at 800 and 900 °C. Furthermore, X-ray absorption spectroscopy showed that the loading of the CoPC precursor influenced the structure of the active sites in the pyrolyzed CoPC/C materials. Overall, this study highlights the importance of the dispersion of CoPC when forming a material that is catalytically active for CO2ERR after pyrolysis.

Oxygen vacancy optimization of the titanium carbide MXene surface for enhanced electrochemical nitrogen reduction

Electrochemical N2 reduction reaction (NRR) provides a hopeful way for sustainable NH3 production. It is the key to realize efficient NRR reaction to optimize the structure and electronic configuration of catalyst materials. Increasing the number of active centers in Ti3C2Tx MXene allows for the development of effective NRR electrocatalysts. Herein, we rationally integrated defect engineering to create oxygen vacancy-rich Ti3C2-MXene (K-Ti3C2-400) as an efficient NRR catalyst with an NH3 yield of 32.25 ± 0.8 μg·h−1·mg−1cat. at − 0.55 V and a Faradaic efficiency of 12.85 % ± 0.26 % at −0.45 V versus reversible hydrogen electrode. According to the density functional theory, oxygen vacancies can prevent the hydrogen evolution reaction by delaying H adsorption, thereby activating absorbed N2 and encouraging *N2H synthesis. This research opens up new possibilities for creating MXene-based catalysts with surface reactivity and selectivity for electrochemical N2 fixation.