Electro-reductive C-H cyanoalkylation of quinoxalin-2(1H)-ones

Herein,we report a practical electro-reductive protocol for the direct C-H cyanoalkylation of quinoxalin-2(1 H)-ones via iminyl radical-mediated ring opening.These mild reactions proceed under metal-,reductant-,and reagent-free conditions to provide synthetically useful cyanoalkylated quinoxalin-2(1 H)-ones.

Ionic liquids for CO_(2) electrochemical reduction

Electrochemical reduction of CO_(2) is a novel research field towards a CO_(2)-neutral global economy and combating fast accelerating and disastrous climate changes while finding new solutions to store renewable energy in value-added chemicals and fuels.Ionic liquids(ILs),as medium and catalysts(or supporting part of catalysts)have been given wide attention in the electrochemical CO_(2) reduction reaction(CO_(2) RR)due to their unique advantages in lowering overpotential and improving the product selectivity,as well as their designable and tunable properties.In this review,we have summarized the recent progress of CO_(2) electro-reduction in IL-based electrolytes to produce higher-value chemicals.We then have highlighted the unique enhancing effect of ILs on CO_(2) RR as templates,precursors,and surface functional moieties of electrocatalytic materials.Finally,computational chemistry tools utilized to understand how the ILs facilitate the CO_(2) RR or to propose the reaction mechanisms,generated intermediates and products have been discussed.

Direct electrochemical reduction of copper sulfide in molten borax

In this study,for the first time,direct copper production from copper sulfide was carried out via direct electrochemical reduction method using inexpensive and stable molten borax electrolyte.The effects of current density(100–800 mA/cm^2)and electrolysis time(15–90 min)on both the cathodic current efficiency and copper yield were systematically investigated in consideration of possible electrochemical/chemical reactions at 1200℃.The copper production yield reached 98.09%after 90 min of electrolysis at a current density of 600 mA/cm^2.Direct metal production was shown to be possible with 6 kWh/kg energy consumption at a 600 mA/cm2 current density,at which the highest current efficiency(41%)was obtained.The suggested method can also be applied to metal/alloy production from single-and mixed-metal sulfides coming from primary production and precipitated sulfides,which are produced in the mining and metallurgical industries during treatment of process solutions or wastewaters.

Gas-phase electrocatalytic conversion of CO_2 to chemicals on sputtered Cu and Cu–C catalysts electrodes

A novel gas-phase electrocatalytic cell containing a low-temperature proton exchange membrane(PEM)was developed to electrochemically convert CO_2into organic compounds.Two different Cu-based cathode catalysts(Cu and Cu–C)were prepared by physical vapor deposition method(sputtering)and subsequently employed for the gas-phase electroreduction of CO_2at different temperatures(70–90°C).The prepared electrodes Cu and Cu–C were characterized by X-ray diffraction(XRD),X-ray photoemission spectroscopy(XPS)and scanning electron microscopy(SEM).As revealed,Cu is partially oxidized on the surface of the samples and the Cu and Cu–C cathodic catalysts were comprised of a porous,continuous,and homogeneous film with nanocrystalline Cu with a grain size of 16 and 8 nm,respectively.The influence of the applied current and temperature on the electro-catalytic activity and selectivity of these materials was investigated.Among the two investigated electrodes,the pure Cu catalyst film showed the highest CO_2specific electrocatalytic reduction rates and higher selectivity to methanol formation compared to the Cu–C electrode,which was attributed to the higher particle size of the former and lower Cu O/Cu ratio.The obtained results show potential interest for the possible use of electrical renewable energy for the transformation of CO_2into valuable products using low metal loading Cu based electrodes(0.5 mg Cu cm^(-2))prepared by sputtering.

Electrochemical preparation of the Fe-Ni36 Invar alloy from a mixed oxides precursor in molten carbonates

The Fe-Ni36 alloy was prepared via the one-step electrolysis of a mixed oxides precursor in a molten Na2CO3-K2CO3 eutectic melt at 750℃,where porous Fe_(2)O_(3)-NiO pellets served as the cathode and the Ni10 Cu11 Fe alloy was an inert anode.During the electrolysis,Ni O was preferentially electro-reduced to Ni,then Fe_(2)O_(3)was reduced and simultaneously alloyed with nickel to form the Fe-Ni36 alloy.Different cell voltages were applied to optimize the electrolytic conditions,and a relatively low energy consumption of 2.48 k W·h·kg^(-1) for production of Fe Ni36 alloy was achieved under 1.9 V with a high current efficiency of 94.6%.The particle size of the alloy was found to be much smaller than that of the individual metal.This process provides a low-carbon technology for preparing the Fe-Ni36 alloy via molten carbonates electrolysis.

Surface regulated Ni nanoparticles on N-doped mesoporous carbon as an efficient electrocatalyst for CO_(2)reduction

Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.

Electrolytic production of Cu-Ni alloys in CaCl_2-Cu_2S-NiS molten salt

An alternative metal/alloy production method,known as direct electrochemical reduction(DER),was introduced for the fabrication of CuNi alloys from mixed sulfides(Cu2S,NiS)under both galvanostatic and potentiostatic conditions.The influences of the process parameters(e.g.,cell voltage and current)on the compositions of the reduced compounds were investigated to yield industrially desirable alloys,namely,CuNi10,CuNi20,and CuNi30.The electrochemical behaviors of Cu2S and NiS in CaCl2 melt were examined at a temperature of 1200°C via cyclic voltammetry(CV).Based on the CV results,the cathodic reduction of Cu2S occurred in one step and cathodic reductions of NiS occurred in two steps,i.e.,Cu2S?Cu for copper reduction and NiS?Ni3S2?Ni for nickel reduction.Galvanostatic studies revealed that it was possible to fabricate high-purity CuNi10 alloys containing a maximum sulfur content of 320×10-6 via electrolysis at 10 A for 15 min.Scanning electron microscopy along with energy-dispersive X-ray spectrometry and optical emission spectroscopy(OES)examinations showed that it was possible to fabricate CuNi alloys of preferred compositions and with low levels of impurities,i.e.,less than 60×10-6 sulfur,via DER at 2.5 V for 15 min.

Electrolysis of Converter Matte in Molten CaCl₂-NaCl

The electrolytic production of nickel-copper alloy by electrochemical reduction of converter matte in molten salt has been investigated. The sintered solid porous pellets of Ni3S2, Cu2S and converter matte were electrolyzed at a voltage of 3.0 V in molten CaCl2-NaCl under the protection of argon gas at 700℃, respectively. The electro-reduction processes were investigated and the products were characterized. The results show that the molten salt electro-reduction process can be used to produce nickel, copper and nickel-copper alloy directly from Ni3S2, Cu2S and converter matte precursors in molten CaCl2-NaCl, respectively. CaS would be formed as the intermediate compound during the electro-reduction process, and then the formed CaS can be gradually decomposed and removed with the increase of the electrolysis time. The experimental results show that the molten salt electro-reduction process has the potential to be used for the reduction of sulfide minerals in molten CaCl2-NaCl.

Carbon dots modified nanoflower petals with super enhanced nitrogen electro-reduction efficiency

Nitrogen electro-reduction reaction(NERR)is a promising alternative method for ammonia production to the Haber-Bosch approach due to mild reaction conditions and free harmful by-product emission.A formidable challenge in bringing NERR closer to the practical application is developing an electrocatalyst which can simultaneously improve the Faraday efficiency and reduce the reaction over-potential.Herein,we fabricated a catalyst of nitrogen-doped carbon dots modified copper-phosphate nanoflower petals(Cu Po-NCDs NF)via a self-assembly method.The flower structure endowed the Cu Po-NCDs NF with large specific surface area,and thus enabled more active sites to be exposed.In particular,we demonstrated that the NCDs modified Cu Po petals with flower-like structure can accelerate the interfacial proton-electron transfer,suppressing the competing hydrogen evolution reaction and promoting the desired NERR process.Ultimately,for the CuPo-NCDs NF catalyzed NERR,the FE_(NH_(3))and the reaction potential both were boosted,the resultant energy efficiency of NERR reached a record-breaking value of 56.5%,and the NH_(3)yield rate increased by 7 times compared to NCDs.This study provides a novel catalyst with a new pathway to boost the NERR.

Precise electro-reduction of alkyl halides for radical defluorinative alkylation

Reported here is a precise electro-reduction strategy for radical defluorinative alkylation towards the synthesis of gem-difluoroalkenes from α-trifluoromethylstyrenes. According to the redox-potential difference of the radical precursors, direct or indirect electrolysis is respectively adopted to realize the precise reduction. An easy-to-handle, catalyst-and metal-free condition is developed for the reduction of alkyl radical precursors that are generally easier to be reduced than α-trifluoromethylstyrenes,while a novel electro-Ni-catalytic system is established for the electro-reduction of alkyl bromides or chlorides towards the electrochemical synthesis of gem-difluoroalkenes. The merit of this protocol is exhibited by its mild conditions, wide substrate scope, and scalable preparation. Mechanistic studies and DFT calculations proved that the coordination of α-trifluoromethylstyrenes to Ni-catalyst prevents the direct reduction of the alkene and, in turn, promotes the activation of alkyl bromide through halogen atom transfer mechanism.

Nitric oxide assists nitrogen reduction reaction on 2D MBene: A theoretical study

Electrocatalytic synthesis of ammonia as an environment-friendly and sustainable development method has received widespread attention in recent years.Two-dimensional(2D)materials are a promising catalyst for ammonia synthesis due to their large surface area.In this work,we have constructed a series of 2D metal borides(MBenes)with transition metal(TM)defects(TMd-MBenes)and comprehensively calculated the reactivity of electrocatalytic synthesis of ammonia-based on density functional theory.The results have demonstrated that the TMd-MBenes can effectively activate nitrogen oxide(NO)and nitrogen(N2)molecules thermodynamically.Particularly interesting,the co-chemisorption of O atoms,dissociated from NO,can facilitate the spilled of the inert N2 molecules into single N atoms,which can further hydrogenate into ammonia easily with an ultralow limiting potential of 0.59 V on TMd-MnB.Our research has not only provided clues for catalyst design for experimental study but also paved the way for the industrial application of electrocatalytic ammonia synthesis.

Dynamic structure change of Cu nanoparticles on carbon supports for CO_(2) electro-reduction toward multicarbon products

Cu nanoparticles with different sizes,morphology,and surface structures exhibit distinct activity and selectivity toward CO_(2) reduction reaction,while the reactive sites and reaction mechanisms are very controversial in experiments.In this study,we demonstrate the dynamic structure change of Cu clusters on graphite-like carbon supports plays an important role in the multicarbon production by combining static calculations and ab-initio molecular dynamic simulations.The mobility of Cu clusters on graphite is attributed to the near-degenerate energies of various adsorption configurations,as the interaction between Cu atoms and surface C atoms is weaker than that of Cu-Cu bonds in the tight cluster form.Such structure change of Cu clusters leads to step-like irregular surface structures and appropriate interparticle distances,increasing the selectivity of multicarbon products by reducing the energy barriers of C-C coupling effectively.In contrast,the large ratio of edge and corner sites on Cu clusters is responsible for the increased catalytic activity and selectivity for CO and H_(2) compared with Cu(100)surface,instead of hydrocarbon products like methane and ethylene.The detailed study reveals that the dynamic structure change of the catalysts results in roughened surface morphologies during catalytic reactions and plays an essential role in the selectivity of CO_(2) electro-reduction,which should be paid more attention for studies on the reaction mechanisms.

Efficient and selective electro-reduction of nitrobenzene by the nano-structured Cu catalyst prepared by an electrodeposited method via tuning applied voltage

Pollution caused by toxic nitrobenzene has been a widespread environmental concern. Selective reduction of nitrobenzene to aniline is beneficial to further efficient and cost-effective biologic treatment. Electro- chemical reduction is a promising method and Cu-based catalysts have been found to be an efficient cathode material for this purpose. In this work, Cu catalysts with different morphologies were fabricated on Ti plate using a facile electrodepositon method via tuning the applied voltage. The dendritic nano-structured Cu catalysts obtained at high applied voltages exhibited an excellent efficiency and selectivity toward the reduction of nitro- benzene to aniline. Effects of the working potential and initial nitrobenzene concentration on the selective reduction of nitrobenzene to aniline using the Cu/Ti electrode were investigated. A high rate constant of 0.0251 mini and 97.1% aniline selectivity were achieved. The fabri- cated nano-structured Cu catalysts also exhibited good stability. This work provides a facile way to prepare highly efficient, cost-effective, and stable nano-sWuctured electro- catalysts for pollutant reduction.

Electro-reduction of Tetraphenylporphyrin (H_2TPP) and Its Eu(Ⅲ)-TPP Complex in Acetone——The Influence of Dissolved Oxygen

1 Introduction It is rather difficult for the rare earth ions to form complex with water-soluble porphyrins （e.g.TPPS4） in aqueous solution. In this note the formation of Eu（Ⅲ）TPP is conducted by introducing equal-molar concentrations of Eu（ClO4）3 and H2TPP into an acetone solution with 0.1 mol/L TEAP to obtain the 1: 1 complex. This complex is reduced with a peak potential at -0.28 V （vs. Ag/AgCl） in voltammetry, and it is found out that Eu3+-TPP is reduced to Eu2+-TPP. The height of the peak is directly propor-

Koutecky-Levich analysis applied to nanoparticle modified rotating disk electrodes： Electrocatalysis or misinterpretation？

The application of naive Koutecky-Levich analysis to micro- and nano-particle modified rotating disk electrodes of partially covered and non-planar geometry is critically analysed. Assuming strong overlap of the diffusion fields of the particles such that transport to the entire surface is time-independent and one-dimensional, the observed voltammetric response reflects an apparent electrochemical rate o constant koapp, equal to the true rate constant ko describing the redox reaction of interest on the surface of the nanoparticles and the ratio,ψ, of the total electroactive surface area to the geometric area of the rotating disk surface. It is demonstrated that Koutecky-Levich analysis is applicable and yields the expected plots of I-1 versus ω-1 where I is the current and ω is the rotation speed but that the values of the electrochemical rate constants inferred are thereof koapp, not ko. Thus, for ψ 〉 1 apparent electrocatalysis might be naively but wrongly inferred whereas for ψ 〈 1 the deduced electrochemical rate constant will be less than ko. Moreover, the effect of ψ on the observed rotating disk electrode voltammograms is significant, signalling the need for care in the overly simplistic application of Koutecky-Levich analysis to modified rotating electrodes, as is commonly applied for example in the analysis of possible oxygen reduction catalysts.

Direct Reduction of Solid Fe_2O_3 in Molten CaCl_2 by Potentially Green Process

Sintered （300℃） porous pellets of Fe2O3 were electrolyzed to Fe in molten CaCl2 （800-900℃） under argon at 1.8-3.2 V for 2-20 h. The laboratory scale experiments show that it was a potentially direct green method to produce Fe powder. At lower electrolysis voltage （〈2.2 V）, higher current efficiency （〉90%） and smaller energy consumption （-3.0 kWh/kg） can be obtained. When the electrolysis voltage was above 2.4 V, the deposition of metal Ca from the salt lowered the current efficiency and increased the energy consumption. The electrolysis voltage also had effects on the micrographs of the reduced powder. The cubic particles can be seen in the products at the voltage lower than 2.2 V; when the voltage was higher than 2.2 V, it was nodular. The reduction proceeds at the cathode in two steps, i.e., from Fe2O3 to FeO and then to Fe. The oxygen emits at the anode. The process is potentially free of carbon emission and produces two useful products at both cathode and anode, promising a zero-emission technology for the extractive metallurgical industry.

Electrochemical Reduction of Nitrobenzene in Ionic Liquid BMImAc

Ionic liquid,1-butyl-3-methylimidazolium acetate（BMImAc）,was used in the electrochemical reduction of nitrobenzene.The electro-reduction of nitrobenzene on platinum electrode was studied by cyclic voltammetry（CV）,in situ Fourier transform infrared（FTIR） spectroscopy and constant-potential electrolysis.The experimental results show that electrochemical reduction process of nitrobenzene was controlled by diffusion,the main reduction product was azobenzen at-1.45 V,and the influences of scan rate and temperature on the electrochemical behaviors were obviously.A reduction mechanism of nitrobenzene in an ionic liquid was a probable ‘nitrobenzene→nitrosobenzene→azobenzene→aniline＇ main reductive reaction route.

Rare earth metal oxides as BH_4^--tolerance cathode electrocatalysts for direct borohydride fuel cells

Rare earth metal oxides（REMO） as cathode electrocatalysts in direct borohydride fuel cell（DBFC） were investigated.The REMO electrocatalysts tested showed favorable activity to the oxygen electro-reduction reaction and strong tolerance to the attack of BH 4-in alkaline electrolytes.The simple membraneless DBFCs using REMO as cathode electrocatalyst and using hydrogen storage alloy as anodic electrocatalyst exhibited an open circuit of about 1 V and peak power of above 60 mW/cm 2.The DBFC using Sm 2 O 3 as cathode electrocatalyst showed a relatively better performance.The maximal power density of 76.2 mW/cm 2 was obtained at the cell voltage of 0.52 V.