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.

Flexible free-standing graphene-like film electrode for supercapacitors by electrophoretic deposition and electrochemical reduction

Electrophoretic deposition in conjunction with electrochemical reduction was used to make flexible free-standing graphene-like films. Firstly, graphene oxide （GO） film was deposited on graphite substrate by electrophoretic deposition method, and then reduced by subsequent electrochemical reduction of GO to obtain reduced GO （ERGO） film with high electrochemical performance. The morphology, structure and electrochemical performance of the prepared graphene-like film were confirmed by SEM, XRD and FT-IR. These unique materials were found to provide high specific capacitance and good cycling stability. The high specific capacitance of 254 F/g was obtained from cyclic voltammetry measurement at a scan rate of 10 mV/s. When the current density increased to 83.3 A/g, the specific capacitance values still remained 132 F/g. Meanwhile, the high powder density of 39.1 kW/kg was measured at energy density of 11.8 W-h/kg in 1 mol/L H2SO4 solution. Furthermore, at a constant scan rate of 50 mV/s, 97.02% of its capacitance was retained for 1000 cycles. These promising results were attributed to the unique assembly structure of graphene film and low contact resistance, which indicated their potential application to electrochemical capacitors.

Electrochemical reduction process of Co(Ⅱ) in citrate solution

Effects of citrate concentration and pH on the electrochemical reduction process of Co（Ⅱ） were investigated by cyclic voltammetry（CV） and electrochemical impedance spectroscopy（EIS）. The results show that Co（Ⅱ） is reduced into two species which are free Co2＋ and [Co（C6H607）] in the solution composed of 0.05 mol/L CoS04·5H2O, 0.20 mol/L Na2SO4 and 0-0.40 mol/L C6H5O7Na3·2H2O in the pH range of 3-9. The reduction behavior depends on the pH of the solution. Co（H） is mainly reduced into the form of free Co^2＋ at pH 3 and into the form of [Co（C6H6O7）] at the pH range of 4-6 in citrate solution. The [Co（C6H6O7）] is first reduced to an intermediate state and then to Co°. Adsorption of the intermediate state exists on the surface of the electrode. Co（Ⅱ） is difficult to be reduced in the solution with the pH above 7, because the existing Co（Ⅱ）-citrate complex species [Co（C6H5O7）]- and [Co（C6H4O7）]2- are more difficult to be reduced than the hydrogen ion.

Coating titanium on carbon steel by in-situ electrochemical reduction of solid TiO_2 layer

Ti coating on A3 steel was successfully prepared by direct electrochemical reduction of high-velocity oxy-fuel （HVOF） thermally sprayed and room-temperature dip-coating titanium dioxide coating on A3 steel in molten CaCl2 at 850 ℃. The interfacial microstructure and mutual diffusion between coating and steel substrate were investigated using scanning electron microscopy （SEM） and energy dispersive X-ray （EDX） spectroscopy. The results show that the precursory TiO2 coating prepared by HVOF has closer contact and better adhesion with the A3 steel substrate. After electrolysis, all of the electro-generated Ti coatings show intact contact with the substrates, regardless of the original contact situation between TiO2 layer and the steel substrate in the precursors. The inter-diffusion between the iron substrate and the reduced titanium takes place at the interface. The results demonstrate the possibility of the surface electrochemical metallurgy （SECM） is a promising surface engineering and additive manufacturing method.

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.

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.

Electrochemical reduction mechanism of Zn^(2+)in molten NaCl-KCl eutectic

A process comprising selective chlorination and molten salt electrolysis was proposed to develop an efficient and environmental-friendly technology for zinc recovery from metallurgical dusts.The theoretical feasibility of this technology was firstly estimated based on thermodynamic fundamentals.Subsequently,the electrochemical behavior of Zn^(2+)on tungsten electrode was investigated in molten NaCl-KCl eutectic at 973 K by many electrochemical transient methods.The results showed that the reduction of Zn^(2+)on tungsten electrode was found to be a one-step process exchanging two electrons with the initial reduction potential of-0.74 V(vs Ag/AgCl),and the electrode process was considered as quasi-reversible and controlled by diffusion.The diffusion coefficient of Zn^(2+)ions in the melts was determined in the order of 10^(-5)cm^(2)/s.Finally,the electrolytic preparation of zinc was carried out by potentiostatic electrolysis in molten NaCl-KCl-ZnCl_(2)eutectic at-1.6 V(vs Ag/AgCl).Spheroidic granular metal with silver-white luster was attained after electrolysis for 9.5 h,and identified as pure Zn.The present study confirms that it is practically feasible to extract pure zinc metal by direct electrolysis of ZnCl_(2)in molten NaCl-KCl eutectic,and provides a valuable theoretical reference for the efficient recovery of zinc from metallurgical dusts.

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.

Thermodynamic Analysis of Desulfurization of Fine Coal by Electrochemical Reduction Flotation

Problems in desulfurization of coal by electrochemical reduction is analyzed and calculated. The result shows that 1 ) the △rGm function of the reaction of pyrite into FeS and the modifying reaction decreasing the oxygenous functions on coal surface is smaller than zero in a spontaneous reaction, and greater than zero in a non-spontaneous reaction; 2) the △rGm value can be adjusted by pH and the dosage of electrolyte to make it be greaterthan zero , which is favorable for the modifying reaction and useful for desulfurization of coal. The research has provided a theoretical foundation for determining reasonable technical parameters of desulfurization。

Indirect Electrochemical Reduction of Indanthrene Brilliant Green FFB

The indirect electrochemical reduction of Indanthrene Brilliant Green FFB （IBG） was investigated in detail by cyclic voltammetry and electrolytic experiments.Triethanolamine （TEA） was used as ligand to form elec-trochemically active Fe（III）-complexes in alkaline solution.The effects of operating parameters including reaction temperature,current density,concentration of NaOH and Fe（III）-TEA mediator had been studied by orthogonal ex-periments and the mechanism of radicals on electrochemical reduction was discussed.The cyclic voltammetry ex-perimental results show that Fe（III）-TEA complexes are well suited for the indirect electrochemical reduction of IBG.The electrolytic experiments show that high current efficiency （49.9%） can be successfully achieved under op-timized conditions and the current density is found to be the main influence factor.

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.

Dechlorination by combined electrochemical reduction and oxidation

Chlorophenols are typical priority pollutants listed by USEPA (U.S. Environmental Protection Agency). The removal of chlorophenol could be carried out by a combination of electrochemical reduction and oxidation method. Results showed that it was feasible to degrade contaminants containing chlorine atoms by electrochemical reduction to form phenol, which was further degraded on the anode by electrochemical oxidation. Chlorophenol removal rate was more than 90% by the combined electro- chemical reduction and oxidation at current of 6 mA and pH 6. The hydrogen atom is a powerful reducing agent that reductively dechlorinates chlorophenols. The instantaneous current efficiency was calculated and the results indicated that cathodic reduction was the main contributor to the degradation of chlorophenol.

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.