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.

Preparation and electrochemical characterization of C/PANI composite electrode materials

Taking the nano-sized carbon black and aniline monomer as precursor and （NH4）2S2O6 as oxidant, the well coated C/polyaniline（C/PANI） composite materials were prepared by in situ polymerization of the aniline on the surface of well-dispersed nano-sized carbon black for supercapacitor. The micro-structure of the C/PANI composite electrode materials were analyzed by SEM. The electrochemical properties of C/ PANI and PANI composite electrode were characterized by means of the galvanostatic charge-discharge experiment, cyclic voltammetric measurement and impedance spectroscopy analysis. The results show that by adding the nano-sized carbon black in the process of chemical polymerization of the aniline, the polyaniline can be in situ polymerized and well-coated onto the carbon black particles, which may effectively improve the aggregation of particles and the electrolyte penetration. What’s more , the maximum of specific capacitance of C/PANI electrode 437.6F·g -1 can be attained. Compared with PANI electrode, C/PANI electrode shows more desired capacitance characteristics, smaller internal resistance and better cycle performance.

Enhancing ammonia production rates from electrochemical nitrogen reduction by engineering three-phase boundary with phosphorus-activated Cu catalysts

Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.

A cascade of in situ conversion of bicarbonate to CO_(2) and CO_(2) electroreduction in a flow cell with a Ni-N-S catalyst

Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.

Degradation study on tin- and bismuth-based gas-diffusion electrodes during electrochemical CO_(2) reduction in highly alkaline media

This work investigated the degradation of tin – based gas-diffusion electrodes (GDE) and also a promising Bi2O3 GDE in electrochemical CO_(2) reduction in highly alkaline media which has not been studied before. The contributions of the electrode wetting (or flooding, if excessively) and catalyst leaching on the degradation were analyzed. Therefore, electrochemical impedance spectroscopy was used to monitor the wetted surface area of the GDE in combination with post-mortem analysis of the penetration depth by visualizing the electrolyte’s cation in the GDE cross-section. Furthermore, to reveal a possible degradation of the electrocatalyst, its distribution was mapped in the GDEs cross-section after operation while the catholyte was additionally analyzed via ICP-MS. The results clearly demonstrate that the SnO_(2) catalyst dissolves in the reaction zone inside the GDE and might be partially redeposited near the GDEs surface. Since the redeposition process occurs only partially a steady loss of catalyst was observed impeding a clear distinction of the two degradation phenomena. Nevertheless, the deterioration of the electrode performance measured as faraday efficiency (FE) of the parasitic hydrogen evolution reaction (HER) qualitatively correlates with the differential double layer capacitance (Cdl). A significant difference of the rate of increase for the hydrogen FE and Cdl can be ascribed to the superposition of both above-mentioned degradation mechanisms. The demonstrated instability of SnO_(2) contrasts with the behavior of Bi2O3 GDE which is stabilized during CO_(2) conversion by redeposition of the diluted dissolved species as metallic Bi which is active for the CO_(2) reduction reaction.

Preliminary study on electrochemical reduction of carbon dioxide on nickel and platinum electrodes

The electrochemical reduction of carbon dioxide was investigated on nickel and platinum electrodes in 0.5 mol dm^-3 KHCO3 solutions. The main products were formic acid and carbon monoxide during the electroreduction of CO2, and the Faradaic efficiency for this process depended on the characteristics of the electrode. At ambient temperature and pressure, the Faradaic efficiency was measured to be 8.6% and 2.5 % respectively for the production of formic acid and CO with Pt electrode at - 1.3V vs Ag/AgCl （saturated KCl）. At this same potential, the Faradaic efficiency was measured to be 8.9% and 1.7% respectively with Ni electrode. Tafel plots showed that the electrochemical reduction of CO2 was not limited by the mass transfer process in the range of -0.8 to - 1.2V vs Ag/AgCl （saturated KCl）.

Effects of current density on preparation and performance of Al/conductive coating/α-PbO_2-Ce O_2-TiO_2/β-Pb O_2-MnO_2-WC-ZrO_2 composite electrode materials

Al/conductive coating/α-Pb O2-Ce O2-Ti O2/β-PbO 2-MnO 2-WC-Zr O2 composite electrode material was prepared on Al/conductive coating/α-PbO 2-Ce O2-Ti O2 substrate by electrochemical oxidation co-deposition technique. The effects of current density on the chemical composition, electrocatalytic activity, and stability of the composite anode material were investigated by energy dispersive X-ray spectroscopy（EDXS）, anode polarization curves, quasi-stationary polarization（Tafel） curves, electrochemical impedance spectroscopy（EIS）, scanning electron microscopy（SEM）, and X-ray diffraction（XRD）. Results reveal that the composite electrode obtained at 1 A/dm2 possesses the lowest overpotential（0.610 V at 500 A/m2） for oxygen evolution, the best electrocatalytic activity, the longest service life（360 h at 40 °C in 150 g/L H2SO4 solution under 2 A/cm2）, and the lowest cell voltage（2.75 V at 500 A/m2）. Furthermore, with increasing current density, the coating exhibits grain growth and the decrease of content of Mn O2. Only a slight effect on crystalline structure is observed.

High performance and stability of double perovskite-type oxide NdBa0.5Ca0.5Co1.5Fe0.5O5+δas an oxygen electrode for reversible solid oxide electrochemical cell

In this study,we successfully synthesized double perovskite-type oxide NdBa0.5Ca0.5Co1.5Fe0.5O5+δ(NBCCF)using a conventional wet chemical method as the oxygen electrode for reversible solid oxide electrochemical cells(RSOCs).The polarization resistance(Rp)of the composite electrode NBCCFGd0.1Ce0.9O2(GDC)is only 0.079Ωcm^2 at 800℃under air.The single cell based on NBCCF-GDC electrode displays a peak power density of 0.941 W/cm^2 in fuel cell mode and a low Rp value of 0.134Ωcm^2.In electrolysis cell mode,the cell displays an outstanding oxygen evolution reaction(OER)activity and shows current density as high as 0.92 A/cm^2 with 50 vol%AH(Absolute Humidity)at 800℃and applied voltage of 1.3 V.Most importantly,the cell exhibits admirable durability of 60 h both in electrolysis mode and fuel cell mode with distinguished reversibility.All these results suggest that NBCCF is a promising candidate electrode for RSOC.

High-Entropy Perovskite Oxide: A New Opportunity for Developing Highly Active and Durable Air Electrode for Reversible Protonic Ceramic Electrochemical Cells

Reversible proton ceramic electrochemical cell(R-PCEC)is regarded as the most promising energy conversion device,which can realize efficient mutual conversion of electrical and chemical energy and to solve the problem of large-scale energy storage.However,the development of robust electrodes with high catalytic activity is the main bottleneck for the commercialization of R-PCECs.Here,a novel type of high-entropy perovskite oxide consisting of six equimolar metals in the A-site,Pr_(1/6)La_(1/6)Nd_(1/6)Ba_(1/6)Sr_(1/6)Ca_(1/6)CoO_(3−δ)(PLN-BSCC),is reported as a high-performance bifunctional air electrode for R-PCEC.By harnessing the unique functionalities of multiple ele-ments,high-entropy perovskite oxide can be anticipated to accelerate reaction rates in both fuel cell and electrolysis modes.Especially,an R-PCEC utilizing the PLNBSCC air electrode achieves exceptional electrochemical performances,demonstrating a peak power density of 1.21 W cm^(−2)for the fuel cell,while simultaneously obtaining an astonishing current density of−1.95 A cm^(−2)at an electrolysis voltage of 1.3 V and a temperature of 600℃.The significantly enhanced electrochemical performance and durability of the PLNBSCC air electrode is attributed mainly to the high electrons/ions conductivity,fast hydration reactivity and high configurational entropy.This research explores to a new avenue to develop optimally active and stable air electrodes for R-PCECs.

Electrochemical disinfection using the gas diffusion electrode system

A study on the electrochemical disinfection with H202 generated at the gas diffusion electrode （GDE） from active carbon/poly- tetrafluoroethylene was performed in a non-membrane cell. The effects of Pt load and the pore-forming agent content in GDE, and operating conditions were investigated. The experimental results showed that nearly all bacterial cultures inoculated in the secondary effluent from wastewater treatment plant could be inactivated within 30 min at a current density of 10 mA/cm^2. The disinfection improved with increasing Pt load. Addition of the pore-forming agent NH4HCO3 improved the disinfection, while a drop in the pH value resulted in a rapid rise of germicidal efficacy and the disinfection time was shortened with increasing oxygen flow rate. Adsorption was proved to be ineffective in destroying bacteria, while germicidal efficacy increased with current density. The acceleration rate was different, it initially increased with current density. Then decreased, and finally reached a maximum at a current density of 6.7 mA/cm^2. The disinfection also improved with decreasing total bacterial count. The germicidal efficacy in the cathode compartment was approximately the same as in the anode compartment, indicating that the contribution of direct oxidation and the indirect treatment of bacterial cultures by hydroxyl radical was similar to the oxidative indirect effect of the generated H2O2.

High-temperature electrochemical performance and phase composition of Ti_(0.7) Zr_(0.5) V_(0.2) Mn_(1.8-x)Ni_x hydrogen storage electrode alloys

The rapid development of electric vehicles demands the development of high performance nickel metal hydride battery that is able to endure high temperature. The discharge properties of Ti 0.7 Zr 0.5 V 0.2 Mn 1.8- x Ni x ( x =0.4, 0.8, 1.1, 1.4, 1.7)hydrogen storage alloys was investigated and its phase composition was analyzed using X ray diffraction. The results show that the cycling life was improved as the content of nickel increases. When x =0.4, 0.8, 1.1 and 1.4, the main phase is MgZn 2 type C14 Laves phase and the second one is cubic TiNi phase. When x =1.7, the Laves phase structure disappears. EDAS analysis shows that the increase of nickel content is effective in suppressing the dissolution of vanadium component in alloys. [

Adsorption properties of Ⅴ(Ⅳ) on resin-activated carbon composite electrodes in capacitive deionization

Composite electrodes prepared by cation exchange resins and activated carbon(AC)were used to adsorb Ⅴ(Ⅳ)in capacitive deionization(CDI).The electrode made of middle resin size(D860/AC M)had the largest specific surface area and mesoporous content than two other composite electrodes.Electrochemical analysis showed that D860/AC M presents higher specific capacitance and electrical double layer capacitor than the others,and significantly lower internal diffusion impedance.Thus,D860/AC M exhibits the highest adsorption capacity and rate of Ⅴ(Ⅳ)among three electrodes.The intra-particle diffusion model fits well in the initial adsorption stage,while the liquid film diffusion model is more suitable for fitting at the later stage.The pseudo-second-order kinetic model is suited for the entire adsorption process.The adsorption of Ⅴ(Ⅳ)on the composite electrode follows that of the Freundlich isotherm.Thermodynamic analysis indicates that the adsorption of Ⅴ(Ⅳ)is an exothermic process with entropy reduction,and the electric field force plays a dominant role in the CDI process.This work aims to improve our understanding of the ion adsorption behaviors and mechanisms on the composite electrodes in CDI.

Kinetics of CO_2 reduction in KOH/methanol electrolyte on Pb electrode

The electrochemical reduction of CO2 on a Pb electrode was investigated in 0. 1 mol/L KOH/methanol electrolyte at different temperatures and pressures. A graphite electrode was employed as the counter electrode, and an AglAgCl （sat. KCl） electrode was used as the reference electrode. The Tafel plots of the products by the electrochemical reduction of CO2 showed that the formation process of HCOOH differed from that of CO and the reduction of CO2was not limited by the diffusion of CO2 in the investigated potential range. Kinetic analysis indicated that the reaction orders were 0. 573 for electrochemical reduction of CO2 to CO and 0. 671 for CO2 to HCOOH in the cathodic direction.

Innovative strategies toward challenges in PV-powered electrochemical CO_(2)reduction

The solar energy-driven electrochemical CO_(2)reduction to value-added fuels or chemicals is considered as an attractive path to store renewable energy in the form of chemical energy to close the carbon cycle.However,CO_(2)reduction suffers from a number of challenges including slow reaction rates,low selectivity,and low energy conversion efficiency.Recently,innovative strategies have been developed to mitigate this challenges.Especially the development of flow cell reactors with a gas diffusion electrode,ionic liquid electrolytes,and new electrocatalysts have dramatically improved the reaction rates and selectivity to desired products.In this perspective,we highlight the key recent developments and challenges in PVpowered electrochemical CO_(2)reduction and propose effective strategies to improve the reaction kinetics,to minimize the electrical energy losses,and to tune the selectivity of the catalysts for desired products,and then suggest future direction of research and development.

High-Con cent rat ion Electrosynthesis of Formic Acid/Formate from CO_(2):Reactor and Electrode Design Strategies

The electrochemical CO_(2)reduction reaction(CO_(2)RR),driven by renewable energy,provides a potential carbon-neutral avenue to convert CO_(2)into valuable fuels and feedstocks.Conversion of CO_(2)into formic acid/formate is considered one of the economical and feasible methods,owing to their high energy densities,and ease of distribution and storage.The separation of formic acid/formate from the reaction mixtures accounts for the majority of the overall CO_(2)RR process cost,while the increment of product concentration can lead to the reduction of separation cost,remarkably.In this paper,we give an overview of recent strategies for highly concentrated formic acid/formate products in CO_(2)RR.CO_(2)RR is a complex process with several different products,as it has different intermediates and reaction pathways.Therefore,this review focuses on recent study strategies that can enhance targeted formic acid/formate yield,such as the all-solid-state reactor design to deliver a high concentration of products during the reduction of CO_(2)in the electrolyzer.Firstly,some novel electrolyzers are introduced as an engineering strategy to improve the concentration of the formic acid/formate and reduce the cost of downstream separations.Also,the design of planar and gas diffusion electrodes(GDEs)with the potential to deliver high-concentration formic acid/formate in CO_(2)RR is summarized.Finally,the existing technological challenges are highlighted,and further research recommendations to achieve high-concentration products in CO_(2)RR.This review can provide some inspiration for future research to further improve the product concentration and economic benefits of CO_(2)RR.

聚(3,4-乙烯二氧噻吩)/MXene复合材料的制备及电容性能研究

MXene材料具有组分灵活可调、电容量较高等优势在超级电容器储能领域备受关注。采用电化学法制得聚3, 4-乙烯二氧噻吩/Nb_(2)CT_(x) MXene (PEDOT/MXene)复合电极材料。结果表明,在扫描速率为30 mV·s^(-1)时,PEDOT/MXene的面积比电容可达250.21 mF·cm^(-2),当电流密度从0.1 mA·cm^(-2)增加到5 mA·cm^(-2)时,PEDOT/MXene的面积比电容保持率为83.5%,远优于PEDOT的64.1%,并且在100 mV·s^(-1)的扫描速率下循环测试1 000次后初始电容保持率可达84%,表现出良好的倍率性能和稳定性。工作为基于MXene基材料构筑高性能电化学储能界面提供了一定的借鉴。

MnFePBA/rGO/CC复合电极的制备及电化学电容性能

采用共沉淀法在氧化石墨烯(GO)表面原位生长锰铁普鲁士蓝类似物(MnFePBA)纳米颗粒,获得不同MnFePBA和GO质量比(1:0.1,1:0.3,1:0.5)的复合粉体;采用超声喷涂法将MnFePBA/GO复合粉体涂敷在预热的碳布(CC)基底上,并借助化学还原将GO转化成还原氧化石墨烯(rGO),制备出MnFePBA/rGO/CC复合电极,研究了复合电极的微观结构和电化学电容性能。结果表明:当MnFePBA与GO的质量比为1:0.1时,MnFePBA颗粒发生团聚;当二者的质量比为1:0.5时,GO纳米片出现明显堆叠;当二者的质量比为1:0.3时,GO与MnFePBA均匀复合,所制备的MnFePBA/GO/CC复合电极具有最高的比电容、最小的内阻及最快的离子扩散速率,电化学性能最优。当MnFePBA和GO质量比为1:0.3时,化学还原法制备的MnFePBA/rGO/CC复合电极在1 A·g^(-1)电流密度下的比电容由化学还原前的888 F·g^(-1)增加到1032 F·g^(-1);当电流密度从1 A·g^(-1)增大到10 A·g^(-1)时,比电容保持率由化学还原前的44.93%提升至54.55%,且在7 A·g^(-1)电流密度下经过3000圈循环后的比电容保持率仍为94.78%。

多孔炭修饰的吸附催化一体化电极高效电解碳酸氢盐

电解碳酸氢盐体系可避免CO_(2)解吸过程中的能量密集型步骤,更具经济性及技术可行性。但目前阴极存在原位产生CO_(2)快速逃逸现象,CO_(2)不能充分参与反应并导致CO_(2)利用率低等问题,本文将活性炭(activated carbon,AC)作为吸附层修饰电极,与CO_(2)催化材料Ag均匀混合以构建吸附催化一体化电极,有效调控气体扩散电极孔隙结构,同时探究了不同炭材料的CO_(2)吸附特性对电解碳酸氢盐性能的影响。在Ag∶AC=4∶1、Ag纳米颗粒载量为2mg/cm^(2)、全氟磺酸-聚四氟乙烯共聚物(Nafion)质量分数为3.04%时,AC修饰Ag电极具有最高的CO法拉第效率,在100m A/cm^(2)和200m A/cm^(2)电流密度时分别达到59.02%和53.79%。稳定性测试表明该电极能够保持11h的高效运行,CO_(2)利用率达68.61%。证明了AC修饰的催化吸附一体化电极在电解碳酸氢盐体系中可有效吸附CO_(2),提高电化学性能。

自支撑Bi@Cu纳米树电极高效电化学还原CO_(2)制甲酸

利用电化学方法将CO_(2)转化为高值化学品是实现碳中和目标的一条有效途径。制备高性能电极是实现CO_(2)高效转化的关键一环。常规喷涂法所制电极中催化层与集流体间的不良接触会严重影响电催化活性以及稳定性。为此,本研究结合电化学沉积和离子置换反应法,构建了一种原位生长的Bi@Cu纳米树(Bi@Cu NTs)自支撑电极。自支撑纳米树结构在降低界面电阻、确保空间结构稳定的同时,为反应提供了丰富的活性位点和发达的孔隙结构,进而实现CO_(2)分子、电解液离子以及电子的协同传输,并进一步促进电化学CO_(2)转化。实验结果表明,Bi@Cu NTs电极在电化学活性和长期运行稳定性方面表现出色。在–1.4~–0.8 V(vs.RHE)的宽工作电位窗口范围内,甲酸选择性均超过90%;在–1.2 V的工作电位下,该电极同时实现了高达97.9%的甲酸选择性和170.6 mA·cm^(–2)的电流密度。此外,该电极在–1.0 V下经过50 h持续电解,获得了超过90%的平均甲酸选择性及大于110 mA·cm^(–2)的平均电流密度,且性能未见明显衰减,稳定性优异。