Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

Effect of electrolysis voltage on electrochemical reduction of titanium oxide to titanium in molten calcium chloride

The electrochemical reduction of solid TiO2 directly to solid metal is a promising alternative to the current Kroll process. The present work is aimed at studying the effect of electrolysis voltage on the rate of electrochemical reduction. The products of electrochemical reduction of TiO2 and Ti2O were examined using the scanning electron microscopy （SEM） and X-ray diffraction （XRD） techniques. The results show that Ti2O was reduced to low valent titanium oxide at 1.5 -1.7 V, which was the result of ionization of oxygen. TiO2 and Ti20 were reduced to titanium metal at 2.1-3.1 V, which was the co-action of ionization of oxygen and calciothermic reduction. The oxygen content decreased rapidly with voltage increasing from 2.1 to 2.6 V, while it changed little from 2.6 to 3.1 V. The optimized cell voltage was 2.6-3.1 V.

Electrochemical reduction characteristics and mechanism of nitrobenzene compounds in the catalyzed Fe-Cu process

The reduction of the nitrobenzene compounds （NBCs） by the catalyzed Fe-Cu process and the relationship between the electrochemical reduction characteristics of NBCs at copper electrode and reduction rate were studied in alkaline medium（pH=11）. The catalyzed Fe-Cu process was found more effective on degradation of NBCs compared to Master Builder＇s iron. The reduction rate by the catalyzed Fe-Cu process decreased in the following order： nitrobenzene 〉4-chloro-nitrobenzene ≥m-dinitrobenzene ：〉 4-nitrophenol ≥2,4-dinitrotoluene 〉2-nitrophenol. The reduction rate by Master Builder＇s iron decreased in the following order： m-dinitrobenzene ≥4-chloro-nitrobenzene 〉4-nitrophenol 〉2,4-dinitrotoluene ≈nitrobenzene 〉2-nitrophenol. NBCs were reduced directly on the surface of copper rather than by the hydrogen produced at cathode in the catalyzed Fe-Cu process. The reduction was realized by the hydrogen produced at cathode and Fe（OH）2 in Master Builder＇s iron, It is an essential difference in reaction mechanisms between these two technologies. For this reason, the reduction by the catalyzed Fe-Cu depended greatly on NBC＇s electron withdrawing ability.

Electrochemical reduction of CO_2 in solid oxide electrolysis cells

The effort on electrochemical reduction of COto useful chemicals using the renewable energy to drive the process is growing fast recently. In this review, we introduce the recent progresses on the electrochemical reduction of COin solid oxide electrolysis cells（SOECs）. At high temperature, only CO is produced with high current densities and Faradic efficiency while the reactor is complicated and a better sealing technique is urgently needed. The typical electrolytes such as zirconia-based oxides, ceria-based oxides and lanthanum gallates-based oxides, anodes and cathodes are introduced in this review, and the cathode materials, such as conventional metal–ceramics（cermets）, mixed ionic and electronic conductors（MIECs） are discussed in detail. In the future, to gain more value-added products, the electrolyte, cathode and anode materials should be developed to allow SOECs to be operated at temperature range of 573–873 K. At those temperatures, SOECs may combine the advantages of the low temperature system and the high temperature system to produce various products with high current densities.

Rational design of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide

The recent development of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide（CO） has attracted much attention due to their unique activity and selectivity compared to other metal catalysts. Particularly, Cu is the unique electrocatalyst for COelectrochemical reduction with high selectivity to generate a variety of hydrocarbons. In this review, we mainly summarize the recent advances on the rational design of Cu nanostructures, the composition regulation of Cu-based alloys, and the exploitation of advanced supports for improving the catalytic activity and selectivity toward electrochemical reduction of CO. The special focus is to demonstrate how to enhance the activity and selectivity of Cubased electrocatalyst for COreduction. The perspectives and challenges for the development of Cu-based electrocatalysts are also addressed. We hope this review can provide timely and valuable insights into the design of advanced electrocatalytic materials for COelectrochemical reduction.

Electrochemical reduction and electrocrystallization process of B(Ⅲ) in the LiF-NaF-KF-KBF_4 molten salt

The mechanisms of the electrochemical reduction and nucleation process of B（Ⅲ） on the platinum electrode in the LiF-NaF-KF-KBF4 molten salt at 700℃ were first investigated using cyclic voltammetry and chronoamperometry techniques. It was found that the electrochemical reduction of B（Ⅲ） occurs in single-step charge transfer： B（Ⅲ） ＋ 3e → B, and the cathode process is reversible. The electrocrystallization process of B（Ⅲ） is instantaneous.

CNT modified by mesoporous carbon anchored by Ni nanoparticles for CO_(2) electrochemical reduction

The design of novel catalysts for efficient electroreduction of CO_(2) into valueadded chemicals is a promising approach to alleviate the energy crisis.Herein,we successfully modify the carbon nanotube by a layer of mesoporous carbon shell anchored by nickel(Ni)nanoparticles.Ni species effectively enable carbon deposition derived from pyrolysis of surfactant 1-hexadecyl trimethyl ammonium bromide to form a mesoporous carbon shell.At the same time,Ni nanoparticles can be embedded in the mesoporous carbon shell due to the confinement effect.Owing to the dispersive Ni nanoparticles and N-doping active sites of mesoporous carbon,the as-prepared electrocatalyst exhibits exciting catalytic performance for the selective reduction of CO_(2) to carbon monoxide(CO)with a maximum Faradaic efficiency of 98%at a moderate overpotential of−0.81 V(vs.reversible hydrogen electrode)and a high partial current density of 60 mA cm^(−2) in H-cell with an aqueous electrolyte.

Ordered cone-structured tin directly grown on carbon paper as efficient electrocatalyst for CO_(2) electrochemical reduction to formate

The conversion of carbon dioxide to chemicals by the electrochemical reactions(ERC)is an efficient solution to the current energy crisis and excess CO_(2) emissions.It is still a great challenge and of significance to synthesize a highly selective,efficient,and non-noble metal electrocatalyst that facilitates the ERC reaction.A novel triton X-100(C_(14)H_(22)O(C_(2)H_(4)O)n)assisted electrodeposition method was developed to synthesize the ordered cone-structured tin(OCSn)electrocatalysts with controllable morphology and structure.The results suggest that Triton X-100 plays an important role in directing the structure of the Sn electrocatalysts during the electrodeposition process.The OCSn synthesized at 60 m A cm^(-2) achieves the best performances.It selectively catalyzes the ERC on the onset potential about 110 m V lower than Sn synthesized without Triton X-100.In 0.5 M Na HCO_(3),high faradaic efficiency(92%)for formate product on OCSn has been achieved.More prominently,the catalyst presents excellent stability,showing no performance deterioration during 30 h electrolysis.This work provides an efficient,green,and scalable synthesis method of the electrocatalyst for CO_(2) reduction to formate.

Electrochemical Reduction of Oxygen on Multi-walled Carbon Nanotubes Electrode in Alkaline Solution

The multi-walled carbon nanotubes (MWNTs) electrode was constructed using poly-tetrafluoroethylene as binder, and the electrochemical reductive behavior of oxygen in alkaline solution was first examined on this electrode. Compared with other carbon materials, MWNTs show higher electrocatalytic activity, and the reversibility of O2 reduction reaction is greatly improved. The experiments reveal that the electrochemical reduction of O2 to HO2- is controlled by adsorption. The preliminary results illustrate the potential application of MWNTs in fuel cells.

ELECTROCHEMICAL REDUCTION OF TANTALUM IN MOLTEN NaCl KCl-K_(2)TaF_(7)

The cathode process of tantalum ion in molten NaCl-KCl-K_(2)TaF_(7),at 720℃was investigated by three transient electrochemical techniques.The results show that the electroreduction reaction of Ta5*involves a single reversible five electron step.The diffusion coefficients of the complexion containing Tas*measured by above mentioned techniques are alike such as 1.15×10^(-5)by cyclic voltammetry.1.10×10^(-5)by chronopotentiometry and 1.15×10^(-5)by chronoamperometry respectively.The effect of electroactive species containing oxygen on tantalum reduction process was also studied.

Electrochemical Reduction of Yttrium Ions

The cathodic electrode process of Y^(3+) ions on the Mo electrode in the LiCl-KCl molten salt with YCl_3(3wt%) in the temperature range of 450～530℃ has been investigated using cyclic voltammetry and chronopotentiometry.The convolution technique has been applied to the treatment of cyclic voltammogram.The results show that the reduction mechanism of Y^(3+) ion is Y^(3+)+3e=Y,a simple one-step process.The cathodic process is very close to a reversible process under lower scanning rates,and is diffusion-controlled.The cathodic product is an insoluble product.

Electrochemical Reduction Characteristics of α-Nitronaphthalene inSulfuric Acid Solution

The'electrochemical reduction characteristics of α-nitronaphthalene in sulfuric acidsolution were first reported in this paper. The results showed that the 1-amino-5-naphthol can beprepared by electrodeduction from α-nitronaphthalene and reduction peak corresponding to thereaction of α-nitronaphthalene to 1-amino-3-naphthol was in the range of -0.40~0.60V(vs, D.H.E )on the amalgamated copper cathode in the presence of SnCl2 additives. The mechanism of α-nitronaphthalene electroreduction to 1-amino-5-naphthol was also investigated, the overallelectroreduction reaction was composed of two intermediate steps and two intermediate productsexisted in solution. The electrochemical reduction mechanism was similar to that of nitrobenzeneto para-aminophenol.

Electrochemical Reduction of Niobium lons in Molten NaF-CaF_2

The mechanism of the electrochemical reduction of niobium ions in molten NaF-CaF_2 (2 : 1 mol) wasinvestigated by means of cyclic voltammetry and chronoamperometry. It is found that the reduction ofNb ( V ) proceedsintwosteps : Nb ( V)→ Nb (Ⅳ)→Nb ( 0 ) . Theelectrochmical reaction Nb ( Ⅳ) + 4e →Nb( 0 ) is a reversible and diffusion-controlled process.

β-Cyclodextrin Facilitates the Cleavage of Cobalt-Carbon Bonds during the Electrochemical Reduction of Alkylaquabis(dimethylglyoximato)Cobalt(Ⅲ)

The electrochemical reduction of alkylaquabis (dimethylglyoximato)Cobalt(Ⅲ) in the absence and presence of β-Cyclodextrin (β-CD) was inveingated by means of cylic voltammetry. It was found that β-CD facilitates the cleavage of Co-C bond during the reduchon process.

Electrochemical Reduction of Zearalenone

Electrochemical reduction of zearalenone 1 and its derivatives was described. The ratio of a-and b-zearalanol 2 obtained by electrochemical reduction reached 8:1, much higher tan that obtained from catalytic hydrogenation. In addition to of the normal reduction products a rearranged product 5 was isolated. The reduction was supposed to be a electrocatalytical reaction.

Improved catalytic performance of CO_(2) electrochemical reduction reaction towards ethanol on chlorine-modified Cu-based electrocatalyst

Effective electrochemical conversion of CO_(2) to value-added liquid multi-carbon products driven by renewable energy is a promising approach to alleviate excessive CO_(2) emission and achieve large-scale renewable energy storage.However,the selectivity and catalytic activity towards liquid multi-carbon products of CO_(2) electroreduction reaction are still unsatisfactory due to the sluggish C-C coupling process and the formation of complex oxygen-containing intermediates.Hence,designing and fabricating highly effective electrocatalysts is crucial for practical applications in this field.Here,we developed Cl-modified Cu catalyst(Cu-Cl)for efficient electrochemical reduction of CO_(2) to ethanol.The optimal Faradaic efficiency and partial current density of ethanol on the Cu-Cl sample reached 26.2%and 343.2 mA·cm^(-2) at-0.74 V(vs.reversible hydrogen electrode(RHE)),which were 1.66 and 1.76 times higher than those of the catalyst without Cl decoration,outperforming those in most previously reported works.Density functional theory(DFT)calculations revealed that the Cl-modified Cu surface suppressed the parasitic hydrogen evolution reaction(HER)and reduced the energy barrier for the C-C coupling process,making the formation of key intermediates favorable for ethanol production.Thus,the decoration of Cl on the Cu surface facilitated ethanol formation.

Advancements in Catalysts for Electrochemical Nitrate Reduction: A Sustainable Approach for Mitigating Nitrate Pollution: A Review

Nitrate pollution is of great importance in both the environmental and health contexts, necessitating the development of efficient mitigation strategies. This review provides a comprehensive analysis of the many catalysts employed in the electrochemical reduction of nitrate to ammonia, and presents a viable environmentally friendly approach to address the issue of nitrate pollution. Hence, the electrochemical transformation of nitrate to ammonia serves the dual purpose of addressing nitrate pollution in water bodies, and is a useful agricultural resource. This review examines a range of catalyst materials such as noble and non-noble metals, metal oxides, carbon-based materials, nitrogen-doped carbon species, metal complexes, and semiconductor photocatalysts. It evaluates catalytic efficiency, selectivity, stability, and overall process optimization. The performance of catalysts is influenced by various factors, including reaction conditions, catalyst structure, loading techniques, and electrode interfaces. Comparative analysis was performed to evaluate the catalytic activity, selectivity, Faradaic efficiency, current density, stability, and durability of the catalysts. This assessment offers significant perspectives on the structural, compositional, and electrochemical characteristics that affect the efficacy of these catalysts, thus informing future investigations and advancements in this domain. In addition to mitigating nitrate pollution, the electrochemical reduction of nitrate to ammonia is in line with sustainable agricultural methods, resource conservation, and the utilization of renewable energy resources. This study explores the factors that affect the catalytic efficiency, provides new opportunities to address nitrate pollution, and promotes the development of sustainable environmental solutions.

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.

A Cu-Pd alloy catalyst with partial phase separation for the electrochemical CO_(2) reduction reaction

Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single product.Herein,we report a simple fabrication method for a Cu-Pd alloy catalyst for use in a membrane electrode assembly(MEA)-based CO_(2) electrolyzer for the electrochemical CO_(2) reduction reaction(ECRR)with high selectivity for CO production.When the composition of the Cu-Pd alloy catalyst was fabricated at 6:4,the selectivity for CO increased and the production of multi-carbon compounds and hydrogen is suppressed.Introducing a Cu-Pd alloy catalyst with 6:4 ratio as the cathode of the MEAbased CO_(2) electrolyzer showed a CO faradaic efficiency of 92.8%at 2.4 V_(cell).We assumed that these results contributed from the crystal planes on the surface of the Cu-Pd alloy.The phases of the Cu-Pd alloy catalyst were partially separated through annealing to fabricate a catalyst with high selectivity for CO at low voltage and C_(2)H_4 at high voltage.The results of CO-stripping testing confirmed that when Cu partially separates from the lattice of the Cu-Pd alloy,the desorption of~*CO is suppressed,suggesting that C-C coupling reaction is favored.