Electroreduction Process Research Articles

Effect of Ionic Surfactants on Kinetics and Mechanism of the Bi(III) Ion Electroreduction in the Mixed Aqueous–Organic Solutions of Supporting Electrolytes

This work presents the results of a study on the effect of ionic surfactants: cationic hexadecyltriammonium bromide (CTAB) and anionic sodium salt of sulfonic acid (1OSASS) on the Bi(III) electroreduction process in mixed aqueous–organic supporting electrolyte solutions containing methanol. This study showed that the composition of the supporting electrolyte solution, particularly the methanol and surfactant concentrations, significantly affects the mechanism and rate of the Bi(III) ion electroreduction. Analysis of the influence of the indicated factors on the mechanisms and kinetics of metal ion electroreduction can contribute not only to the optimization of industrial electrochemical processes but also to the development of innovative technological solutions, such as advanced electrochemical materials and novel sensors. In these experiments, an innovative electrode made of cyclic renewable liquid silver amalgam (R-AgLAFE) was used as a working electrode, which stands out among classic mercury electrodes (HMDE type) due to the significant reduction in mercury consumption while maintaining similar performance.

Electrochemical recovery of ruthenium via carbon black nano-impacts

The recovery of ruthenium from low-concentration solutions poses a significant challenge due to its scarcity and rising economic value, and nano-impact electrochemistry has emerged as a promising method for efficient recovery of critical metals from solution through deposition during impacts of non-metallic nanoparticles. In this study, we investigate the redox chemistry of ruthenium on carbon black via the impact technique and demonstrate the ability to recover ruthenium from solution. The reduction (electrodeposition) and oxidation of Ru3+ ions in solution onto carbon black nanoparticles can be observed during nano-impacts with the respective onset potentials of these redox processes agreeing with those obtained from solution voltammetry. Upscaled experiments focusing on the electroreduction process, led to the formation of RuOx deposits, confirmed through scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis, X-ray photoelectron spectroscopy (XPS) analysis, and thermogravimetric analysis (TGA). Under partially-optimised conditions, >90 % recovery of Ru(III) from a 1 mM solution was achieved in ca. 8 h.

Metal nitrides as electrocatalysts in green ammonia synthesis

Green ammonia is assumed to be an important part of the European hydrogen economy and one of the most important substrates of chemical industry. The future development of its manufacturing processes can be related to the electrocatalytic studies yielding in the development of the catalytic materials that would effectively break the nitrogen-nitrogen bond to successfully drive the N2RR—a process of molecular nitrogen electroreduction to ammonia. Molecular nitrogen is characterized with strong triple bond energies (942 kJ/mol) which leading into large dissociation energy of N2 (9,76 eV) and also large energy barrier of the first step of triple bond dissociation 410 kJ/mol (4,25 eV). Those large energies makes reduction to ammonia an extremely difficult task. Metal nitrides of d and f block became in interest due to their activity in ammonia production from molecular nitrogen and hydrogen. Practically all the transition elements occurs in one of the four types of crystalline structures: regular, regular face cantered, hexagonal and hexagonal close packed. The reactions of these metals with nitrogen (or ammonia) typically yields in nitride compounds of an identical type of crystalline structure as the initial metal. Dealing with single metal systems, their ternary counterparts and metal–metal nitride heterostructures, the presented review shows that nitrides are promising groups of electrocatalytic materials. Being property-prone to their internal structural features such as non-stoichiometry and correlated concentration of nitrogen vacancies, metal nitrides are a good candidate for joined investigations spanned between electrochemistry, inorganic chemistry and material engineering.

Interface-stabilized high-valent Sn enables efficient CO2 electroreduction to formate/formic acid across the full pH range

The electrocatalytic synthesis of formate/formic acid (HCOO−/HCOOH) from CO2 can mitigate environmental issues and provide high-value-added products. Although tin oxide is an excellent catalyst for HCOO−/HCOOH production, it is easily reduced to its metallic state at high potentials, which decreases its activity. Additionally, tin oxide is challenging to stabilize in acidic electrolytes. Here, we introduced Cu to tin oxide catalysts to form Cu6Sn5@SnOx during the CO2 electroreduction process (CO2RR), achieving a high HCOO−/HCOOH Faradaic efficiency (88.4 % at 800 mA cm−2 in 1 M KOH electrolyte, 87.8 % at 300 mA cm−2 in 0.1 M H2SO4 electrolyte containing 1 M K+) and a maximum HCOO− partial current density (757.5 mA cm−2). The in situ spectroscopy and DFT calculations results revealed that the SnOx/Cu6Sn5 alloy interface plays a crucial role in stabilizing the surface high-valent Sn, which provides a thermodynamically stable environment for adsorbed *OCHO intermediate. This discovery offers new insights into the roles of each component in bimetallic catalysts in CO2 reduction.

Regulating the Water Dissociation on Atomic Iron Sites to Speed Up CO2 Protonation and Achieve pH‐Universal CO2 Electroreduction

AbstractAtomic Fe sites enabled electrochemical carbon dioxide (CO2) reduction (ECO2R) to carbon monoxide (CO) at low overpotentials. However, the narrow potential ranges for selective CO2 conversion on atomic Fe sites hindered the CO production at high current densities. Therefore, unveiling the CO2 electroreduction processes and clarifying the catalytic mechanisms on different atomic Fe sites are important for better design of atomic Fe catalysts toward efficient ECO2R. Herein, the ECO2R processes on single‐atom, dual‐atom, and cluster Fe sites are systematically investigated, and clarify that the balanced water dissociation and CO2 protonation on dual‐atom Fe sites promote the efficient CO production. The dual‐atom Fe catalyst achieves Faradaic efficiencies of CO (FECO) above 92% over a wide potential range of −0.4–−0.9 V versus reversible hydrogen electrode and maintains FECO of 91% after 153‐h electrolysis in H‐type cell. Benefitting from the favorable CO2 protonation for ECO2R on dual‐atom Fe sites, pH‐universal CO2 electroreduction is achieved in alkali‐/acid‐/bicarbonate‐fed membrane electrode assembly electrolyzer, with FECO exceeds 98% in strongly acidic/alkaline and neutral mediums. The work reveals a water dissociation‐promoted CO2 electroreduction on dual‐atom Fe sites and presents a feasible regulation of atomic Fe sites for highly active/selective ECO2R.

Unveiling the Interfacial Species Synergy in Promoting CO2 Tandem Electrocatalysis in Near-Neutral Electrolyte.

The interfacial species-built local environments on Cu surfaces impact the CO2 electroreduction process significantly in producing value-added multicarbon (C2+) products. However, intricate interfacial dynamics leads to a challenge in understanding how these species affect the process. Herein, with ab initio molecular dynamics (AIMD) and finite element method (FEM) simulations, we reveal that the highly concentrated interfacial species, including the *CO, hydroxide, and K+, could synergistically promote the C-C coupling on the one-dimensional (1D) porous hollow structure regulated interfacial environment. The Cu-Ag tandem catalyst was then synthesized with the as-designed structure, exhibiting a high C2+ Faradaic efficiency of 76.0% with a partial current density of 380.0 mA cm-2 in near-neutral electrolytes. Furthermore, in situ Raman spectra validate that the 1D porous structure regulates the concentration of interfacial CO intermediates and ions to increase *CO coverage, local pH value, and ionic field, promoting the CO2-to-C2+ activity. These results provide insights into the design of practical ECR electrocatalysts by regulating interfacial species-induced local environments.

Electrochemical and Photoelectrochemical Reduction of Carbon Dioxide on Ruthenium-Cultured Bacterial Biofilms

Most of the bacterial species form biofilms, in which microorganisms are attached to a surface and they are held together by extracellular polymeric substances that they produce. They tend to grow almost everywhere both on living or non-living surfaces. Biofilms are able to propagate charge within their structures and to transfer effectively electrons at interfaces, as well as they could exhibit electrocatalytic properties (e.g. in Microbial Fuels Cells). The application of microbes provides better flexibility: experiments with fuel cells can be operated at normal conditions (temperatures and pressures). Wide variety of microbial metabolic pathways gives the possibility to use aggregates of bacteria in diverse processes. Proposed electrochemical studies using bacterial biofilms (in the form of thin coatings on the glassy carbon electrodes) can be considered as an attempt to find efficient methods of using the energy produced by microorganisms and converting it to electricity.The ultimate goal of the present research has been to determine whether it is possible under laboratory conditions to perform electrocatalytic processes using the hybrid (composite) layers composed of aggregates of bacteria in pristine or modified forms. A biofilm formed by a strain of Yersinia enterocolitica (Y. enterocolitica) is characterized by a high physicochemical stability over a wide pH range (4-10) and temperatures (0-40°C).The subject of interest is a fairly complex reaction, electroreduction of carbon dioxide. There has been growing interest in the search of electrocatalytic anf photoelectrochemical systems capable of efficient conversion of carbon dioxide into fuels and utility chemicals. Our previously performed studies have clearly shown that the Y. enterocolitica biofilm itself has no activity with respect to reduction of CO2, however it acts as a good matrix for the catalytic (e.g. noble metal or metaloorganic) centers, because it affects the reaction mechanism and appears to decrease overpotential of the electroreduction processes. The conducted research shows that the composite materials containing bacterial biofilms can be successfully used to construct systems that have an electrocatalytic reactivity in the reduction of carbon dioxide. We will also address the possibility of dispersing the organometallic ruthenium (II) complex in the biological layer (biofilm). Indeed, the ruthenium (II) complex has been immobilized in the biofilm matrix by successive modification of the liquid medium (Luria-Bertani medium) for culturing bacteria with a solution of the complex compound. In addition, the biological matrix was used (along with the ruthenium (II) complex molecules dispersed in its layer) as a protective coating, stabilizing the unstable p-type semiconductor - copper (I) oxide. The proposed hybrid co-catalytic system showed activity during the photoelectrochemical reduction of carbon dioxide and stability under semi-neutral experimental conditions. Finally, we are going to address the design of the above-mentioned catalytically active systems emphasizing the need to control the structure of the studied hybrid materials (in addition to their stability). Among important issues is the viability of bacteria in the biological membrane as well as elucidation of the role of the bacterial biofilm during the carbon dioxide reduction.

A Comparative Study of Electrochemical Reduction of Levulinic Acid on Various Electrodes in Organic Solvents.

Studies on the electrochemical hydrogenation (ECH) of levulinic acid (LA) to valeric acid (VA) or γ-valerolactone (GVL) have mainly focused on the electrochemical reduction of LA in acidic aqueous solutions. However, the narrow range of applied potentials has hindered understanding of some mechanistic aspects of LA electrochemical conversion. Earlier, we discovered that employing proton-deficient non-aqueous reaction media provides more comprehensive insights into the mechanism of LA electrochemical reduction. Here, we conducted further investigations into the LA electroreduction process using cyclic voltammetry in various organic solvents on a Pt electrode and on various electrode materials in acetonitrile, both with and without the addition of proton donors. The products of the ECH processes were identified using HPLC. The solvent nature, the presence of proton donors, the electrode material, and the applied potential strongly influence the LA electroreduction process. This study reveals that LA, in the presence proton donors, can undergo electrochemical reduction through different pathways, depending on the difference (ΔE1/2) between the reduction half-wave potential of protons and LA on a certain electrode. When the difference is large, the LA reduction is incomplete and the formation of GVL is observed. Under the close reduction potentials of protons and LA, LA can be completely reduced to VA.

Confined CuⅠ sites in partially electro-reduced 2D conductive Cu-MOF film for boosting CO2 electrocatalysis to C2 products

Cu-based catalysts, especially co-sites of Cu0 and CuⅠ, are the best competitors for electrochemical CO2 fixation to produce multi-carbon (C2 + ) products. However, it is challenging to construct highly stable CuⅠ sites due to the changeability of its valence state and electronic structure in the electroreduction process, and the mechanism is also elusive. Herein, a 2D conductive CuⅡ-MOF film (CuⅡHHTP@Cu0) is prepared on Cu (100) foil by in-situ electrochemical assembly. After pre-reduction, the in-situ produced Cu2O clusters are confined in the cavities of the film created by the local breaking of the MOF framework to construct a unique CuⅠ-CuⅡHHTP@Cu0 catalyst, so that a novel strategy is proposed to stablize highly dispersed CuⅠ sites during electrochemical reduction, thus protecting the Cu2O clusters from further reduction and ensuring the coexistence of CuⅠ (111)-Cu0 (100) sites. As such, the current density of CO2 electrochemical reduction catalyzed by this catalyst exceeds 300 mA cm−2, the duration overs 50 h, and the C2 selectivity achieves 72.6 %. In-situ spectroscopy and theoretical calculations reveal that the optimized microenvironment of the CuⅠ (111) sites reduces the energy barrier of *OCCOH coupling, and Cu0 (100) sites increase the coverage of *CO, thus boosting the production of C2 products.

Proton-Coupled Electron Transfer Mechanisms for CO2 Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine.

Immobilized cobalt phthalocyanine (CoPc) is a highly promising architecture for the six-proton, six-electron reduction of CO2 to methanol. This electroreduction process relies on proton-coupled electron transfer (PCET) reactions that can occur by sequential or concerted mechanisms. Immobilization on a conductive support such as carbon nanotubes or graphitic flakes can fundamentally alter the PCET mechanisms. We use density functional theory (DFT) calculations of CoPc adsorbed on an explicit graphitic surface model to investigate intermediates in the electroreduction of CO2 to methanol. Our calculations show that the alignment of the CoPc and graphitic electronic states influences the reductive chemistry. These calculations also distinguish between charging the graphitic surface and reducing the CoPc and adsorbed intermediates as electrons are added to the system. This analysis allows us to identify the chemical transformations that are likely to be concerted PCET, defined for these systems as the mechanism in which protonation of a CO2 reduction intermediate is accompanied by electron abstraction from the graphitic surface to the adsorbate without thermodynamically stable intermediates. This work establishes a mechanistic pathway for methanol production that is consistent with experimental observations and provides fundamental insight into how immobilization of the CoPc impacts its CO2 reduction chemistry.

Electric Field Generated at the Millisecond Pulse-Polarized Interface Facilitates the Electrolytic Conversion of SO2 into H2S.

Interfacial electric field holds significant importance in determining both the polar molecular configuration and surface coverage during electrocatalysis. This study introduces a methodology leveraging the varying electric dipole moment of SO2 under distinct interfacial electric field strengths to enhance the selectivity of the SO2 electroreduction process. This approach presented the first attempt to utilize pulsed voltage application to the Au/PTFE membrane electrode for the control of the molecular configuration and coverage of SO2 on the electrode surface. Remarkably, the modulation of pulse duration resulted in a substantial inhibition of the hydrogen evolution reaction (HER) (FEH2 < 3%) under millisecond pulse conditions (ta = 10 ms, tc = 300 ms, Ea = -0.8 V (vs Hg/Hg2SO4), Ec = -1.8 V (vs Hg/Hg2SO4)), concomitant with a noteworthy enhancement in H2S selectivity (FEH2S > 97%). A comprehensive analysis, incorporating in situ Raman spectroscopy, electrochemical quartz crystal microbalance, COMSOL simulations, and DFT calculations, corroborated the increased selectivity of H2S products was primarily associated with the inherently large dipole moment of the SO2 molecule. The enhancement of the interfacial electric field induced by millisecond pulses was instrumental in amplifying SO2 coverage, activating SO2, facilitating the formation of the pivotal intermediate product *SOH, and effectively reducing the reaction energy barrier in the SO2 reduction process. These findings provide novel insights into the influences of ion and molecular transport dynamics, as well as the temporal intricacies of competitive pathways during the SO2 electroreduction process. Moreover, it underscores the intrinsic correlation between the electric dipole moment and surface-molecule interaction of the catalyst.

Electrochemical Measurements of the In(III) Ions Electroreduction; the Influence of Mixed Adsorption Layers ACT-CTAB and ACT-SDS

Using voltammetric and impedance methods, the effects of mixed adsorption layers ACT-CTAB and ACT-SDS on the kinetics and mechanism of In(III) ions electroreduction were investigated. Acetazolamide (ACT) was shown to catalyse the course of the electrode reaction (according to the cap-pair rule). The multi-step nature of the In(III) ions electroreduction process in each of the systems studied in the chemical step of formation of the active In(III) - ACT complexes in the adsorption layer playing an important role is demonstrated. The presence of the cationic surfactant CTAB increases the dynamics of acceleration of the In(III) ion electroreduction process by ACT, while the presence of the anionic surfactant SDS inhibits this reaction.

Critical Role of Cu Nanoparticle-Loaded Cu(100) Surface Structures on Structured Copper-Based Catalysts in Boosting Ethanol Generation in CO2 Electroreduction.

Presently, realizing high ethanol selectivity in CO2 electroreduction remains challenging due to difficult C-C coupling and fierce product competition. In this work, we report an innovative approach for improving the efficiency of Cu-based electrocatalysts in ethanol generation from electrocatalytic CO2 reduction using a crystal plane modification strategy. These novel Cu-based electrocatalysts were fabricated by electrochemically activating three-dimensional (3D) flower-like CuO micro/nanostructures grown in situ on copper foils and modifying with surfactants. It was demonstrated that the fabricated Cu-based electrocatalyst featured a predominantly exposed Cu(100) surface loaded with high-density Cu nanoparticles (NPs). The optimal Cu-based electrocatalyst displayed considerably improved CO2 electroreduction performance, with a Faraday efficiency of 37.9% for ethanol and a maximum Faraday efficiency of 68.0% for C2+ products at -1.4 V vs RHE in an H-cell, accompanied by a high current density of 69.9 mA·cm-2, much better than the particulate Cu-based electrocatalyst. It was unveiled that the Cu(100)-rich surface of nanoscale petals with abundant under-coordinated copper atoms from CuNPs was conducive to the formation and stabilization of key *CH3CHO and *OC2H5 intermediates, thereby promoting ethanol generation. This study highlighted the critical role of CuNP-loaded Cu(100) surface structures on structured Cu-based electrocatalysts in enhancing ethanol production for the CO2 electroreduction process.

Preparation of metallic lead from lead sulfide by bagged cathode solid-phase electroreduction in a low-temperature and weakly alkaline solution

Developing a method to recovering metallic lead from lead sulfide at lower temperatures without emitting lead dust and SOx gas holds significant importance in terms of environmental sustainability and economy efficiency. In this study, we employ a bagged cathode to directly produce metallic lead from lead sulfide in a low-cost weakly alkaline electrolyte (200 g/L Na2SO4 + 0.1 mol/L NaOH) at a temperature as low as 40 °C. The use of bagged cathode effectively immobilizes reactants and reduces cathodic polarization, thereby enabling the electro-reduction of lead sulfide under mild conditions. During the electroreduction process, the granular lead sulfide powders gradually undergo transformation into rod- or sheet-like metallic lead, achieving lead recovery ratio and desulfurization rate reaching 96.4 % and 97.9 %, respectively. Cyclic voltammetry analysis confirms that the oxidation reaction of S2− released from cathode is irreversible, thereby not interfering the cathodic electroreduction of lead sulfide. This bagged cathode direct electroreduction method utilizing a low-temperature, weakly alkaline aqueous solution exhibits the potential for application to other sulfides or oxides.

Paper-in-Tip Bipolar Electrospray Mass Spectrometry for Real-Time Chemical Reaction Monitoring.

Capturing short-lived intermediates at the molecular level is key to understanding the mechanism and dynamics of chemical reactions. Here, we have developed a paper-in-tip bipolar electrolytic electrospray mass spectrometry platform, in which a piece of triangular conductive paper incorporated into a plastic pipette tip serves not only as an electrospray emitter but also as a bipolar electrode (BPE), thus triggering both electrospray and electrolysis simultaneously upon application of a high voltage. The bipolar electrolysis induces a pair of redox reactions on both sides of BPE, enabling both electro-oxidation and electro-reduction processes regardless of the positive or negative ion mode, thus facilitating access to complementary structural information for mechanism elucidation. Our method enables real-time monitoring of transient intermediates (such as N,N-dimethylaniline radical cation, dopamine o-quinone (DAQ) and sulfenic acid with half-lives ranging from microseconds to minutes) and transient processes (such as DAQ cyclization with a rate constant of 0.15 s-1). This platform also provides key insights into electrocatalytic reactions such as Fe (III)-catalyzed dopamine oxidation to quinone species at physiological pH for neuromelanin formation.

Stabilizing Cu0/Cu2+ interface by hydroxy-rich amorphous SiO2 for enhanced electrocatalytic CO2 reduction to ethylene

Constructing a stable Cu0/Cu2+ interface is critical for enhancing the C-C coupling during the process of CO2 electroreduction. However, the high-valence Cu species are unstable under the operating conditions. Herein, polyhedral-shaped CuO is coated with hydroxy-rich SiO2 nanoparticles (m-SiO2/CuO) to stabilize the Cu2+ species, enabling efficient CO2 reduction to the ethylene product. Significantly, the optimal m-SiO2/CuO catalyst exhibits an impressive Faradaic efficiency of 55.5 % and an industrial-level partial current density of 500 mA cm−2 toward ethylene. Fourier transform infrared spectra and X-ray photoelectron spectra reveal that the strong interfacial interaction between CuO and hydroxy-rich SiO2 is conducive to stabilizing the Cu2+ species. In-situ characterizations reveal that the Cu0/Cu2+ interface facilitates CO2 activation and the key intermediate *OCCHO, thus promoting the production of ethylene. This work paves the way for developing advanced electro-catalysts of producing ethylene.

Magnetic transition of 1D ferromagnetic catalysts during the NO electroreduction

Exploration of magnetic phase transitions during electrochemical processes is of great importance for rational design of supported magnetic-metal electrocatalysts. Herein, we systematically investigated the magnetic transition between ferromagnetism (FM) and anti-ferromagnetism (AFM) in one-dimensional ferromagnetic Co chain supported on graphene (Co4N8-gra) during NO electroreduction (NORR) process, focusing on the impact of potential and acidity on the catalytic property and magnetic transition. A combination of catalytic kinetics calculations and microkinetic simulations reveals that the Co4N8-gra exhibits excellent NH3 selectivity and thermal stability. In the implicit solvent model, the general reaction follows optimal pathway: * + NO(g) → *NO → *HNO → *H2NO → *H2NOH → *NH2 → *NH3 → * + NH3, with the potential-determining step (PDS) identified as *NO → *HNO. In acidic solvent, the magnetic transitions follow the pathway (FM → AFM2 → AFM2 → AFM2 → AFM1 → AFM1 → AFM1 → FM) under an applied potential of −0.20 V/RHE. In neutral solvent, the magnetic transitions occur according to this pathway (FM → AFM2 → AFM2 → FM → AFM1 → AFM1 → AFM1 → FM) under an applied potential of −0.14 V/RHE. In an alkaline solvent, the magnetic transitions proceed along this sequence (FM → AFM1 → AFM2 → FM → AFM1 → AFM1 → AFM1 → FM) under an ultralow potential of −0.08 V/RHE. Essentially, the improvement of catalytic property is attributed to the synergistic influence of external potential and magnetic-state transition on the adsorption of reaction species (e.g., NO and NH3). Magnetic transitions are closely associated with ligand field effect of metal site with variable valence electron induced by applied potential. In general, this study provides valuable insights for the controllable design of magnetic metal catalysts.

A sequencing electroreduction-electrooxidation system driven by atomic hydrogen for enhancing 2,4-dichloronitrobenzene removal from wastewater

The sequencing electroreduction-electrooxidation process has emerged as a promising approach for the degradation of the chloronitrobenzenes (CNBs) due to its elimination of electro-withdrawing groups in the reduction process, facilitating further removal in the subsequent oxidation process. Herein, we developed a cathode consisting of atom Pd on a Ti plate, which enabled the electro-generation of atomic hydrogen (H*) and the efficient electrocatalytic activation of H2O2 to hydroxyl radical (•OH). Cyclic voltammetry (CV) curves and electron spin resonance (ESR) spectra verified the existence of H* and •OH. The electroreduction-electrooxidation system achieved 94.7% of 20 mg L−1 2,4-DCNB removal with a relatively low H2O2 addition (5 mM). Moreover, the inhibition rate of Photobacterium phosphoreum in the effluent decreased from 95% to 52% after the sequencing electroreduction-electrooxidation processes. It was further revealed that the H* dominated the electroreduction process and triggered the electrooxidation process. Our work sheds light on the effective removal of electron-withdrawing groups substituted aromatic contaminants from water and wastewater.

Modulating surface microenvironment based on Ag-adorned CuO flower-liked nanospheres for strengthening C-‍C coupling during CO2RR

Modulating the surface microenvironment is crucial in strengthening CC coupling, leading to increasing selectivity in the production of multi-carbon (C2+) products during CO2 electroreduction. Herein, we have concentrated on investigating how to control the effect of surface distribution of active components of a series of Ag-decorated CuO, denoted as xAg/yCuO. These catalysts with similar chemical elements and morphology are designed, but they exhibit different selectivity in the CO2 electroreduction process. As a result, the Ag particles in 3Ag/CuO aggregates, while the Ag in 2Ag/2CuO and Ag/3CuO is uniformly distributed on the flower-like CuO nanosphere. Besides, 3Ag/CuO has the highest Faraday efficiency (FE) of CO with a value of 30.9 % at 0.8 V vs. RHE, demonstrating rich-Ag catalysts are beneficial to produce CO. 2Ag/2CuO shows excellent FEC2H4 of 51.4 % at -1.2 V vs. RHE due to the highly dispersed distribution of Ag on the flower-like CuO and higher vacancy O. Ag/3CuO exhibits higher FEH2 compared to other catalysts across a wide potential range, and its minimal impedance is attributed to its exceptional performance in the hydrogen evolution reaction. The proposed reaction pathway for the most effective catalysts 2Ag/2CuO, as determined by in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), involves the following steps: CO2 →*CO2−→ *COOH → *CO→ *CHO→ *OCHCHO→ *OCHCH2→ C2H4. These findings demonstrate that controlling the surface structure can influence the local environment to enhance the efficiency of CO2 electroreduction.

Electrocatalytic reduction of nitrate to ammonia by Pd/In modified Nickel foam electrode in aqueous solution

Nitrate pollution in surface water and ground water has drawn wide attention, which has brought challenges to human health and natural ecology. Electroreduction of nitrate to NH3 in waste water was a way to turn waste into wealth, which has attracted interest of many researchers. Using Nickel foam as substrate, we prepared Pd/In bimetallic electrode (NF–Pd/In) according to a two-step electrodeposition method. There are many irregularly shaped particles in the size range of 10 nm–100 nm accumulated on the surface of prepared NF–Pd/In electrode, which could supply high specific area and more active sites for nitrate electroreduction. FESEM-EDS, XRD and XPS analysis confirmed the uniform distribution of Pd and In on the surface of prepared NF–Pd/In electrode, with a mass ratio of 4.5/1. Above 96% of 100 mg/L NO3−-N was removed and 95% of NH3 selectivity was reached after 5 h of reaction under −1.6 V vs. Ag/AgCl sat. KCl when using 0.05 mol/L of Na2SO4 as electrolyte. High concentration of NaCl (0.05 mol/L) in the test solution dramatically decreased the NH3 selectivity because the produced NH3 could be further oxidized to N2 by the formed HClO from Cl−. EIS tests indicated that the prepared NF–Pd/In electrode showed much lower electrode resistance than NF due to the adsorptive property and electrocatalytic ability for nitrate removal. Density functional theory (DFT) calculations indicated that the presence of In could promote the conversion of NO3− to *NO3 during the process of nitrate electroreduction to NH3. Circulating tests demonstrated the stability of prepared NF–Pd/In electrode.