Electroreduction of CO_(2) into formate catalyzed by metal-organic frameworks(MOFs) is a promising avenue to promote the carbon cycle,but the oxygen evolution reaction(OER) process in anode usually limited the reaction efficiency.Here,a new framework {(Me_(2) NH_(2))[Bi(L)]·4 DMF·2 H_(2) O}_n(V12) was constructed and structurally characterized(L=5,5'-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo [lmn][3,8]phenanthroline-2,7-diyl) dibenzene-1,3-dicarboxylic acid;DMF=N,N-dimethylformamide).V12 possesses large one-dimensional channels with the size of 1.5 × 0.7 nm and exhibits good stability in common solvents.After V12 was modified on electrode via electrodeposition,as-synthesized sample exhibits impressive catalytic performance for the transformation of CO_(2) into formate with Faraday efficiency of93.2% and current density of 11.78 mA cm^(-2) at-0.9 V(vs.RHE).Control experiments revealed that the MOFs electrodeposition strategy significantly improves the charge transfer rate and introduces more structural defects,which promotes the reaction activity.Moreover,tetra hydroisoquinoline is added as an accelerant in the anode to achieve the simultaneous generation of formate and dihydroisoquinoline.More importantly,the cell voltage is reduced from 2.79 to 2.52 V at 10 mA cm^(-2) in a two-electrode system due to more positive reaction kinetics.This work provides an enlightening strategy for using MOFs to establish an effective system to achieve CO_(2) reduction while obtaining high value-added oxidation products.
Active non-noble metal catalysts plays a decisive role for water electrolysis,however,the rational design and development of cost-efficient electrocatalysts with Pt/IrO2-like activity is still a challenging task.Herein,a facile one-step electrodeposition route in deep eutectic solvents(DESs) is developed for morphology-controllable synthesis of cobalt oxide/phosphate-carbon nano hybrids on nickel foam(CoPO@C/NF).A series of CoPO@C/NF nanostructures including cubes,octahedrons,microspheres and nanoflowers are synthesized,which show promising electrocatalytic properties toward oxygen and hydrogen evolution reactions(OER/HER).Such surface self-organized microstructure with accessible active sites make a significant contribution to the enhanced electrochemical activity,and hybridizing cobalt oxide with cobalt pyrophosphates and carbon can result in enhanced OER performance through synergistic catalysis.Among all nanostructures,the obtained microspherical CoPO@C/NF-3 catalyst exhibits excellent catalytic activities for OER and HER in 1.0 M KOH,affording an anodic current density of 10 mA cm^(-2) at overpotentials of 293 mV for OER and 93 mV for HER,with good long-time stability.This work offers a practical route for engineering the high-performance electrocatalysts towards efficient energy conversion and storage devices.
Ni-rich layered cathodes(LiNi_xCo_yMn_(2)O_(2))have recently drawn much attention due to their high specific capacities.However,the poor rate capability of LiNi_xCo_yMn_(2)O_(2),which is mainly originated from the twodimensional diffusion of Li ions in the Li slab and Li^(+)/Ni^(2+)cation mixing that hinder the Li^(+)diffusion,has limited their practical application where high power density is needed.Here we integrated Li_(2)MnO_(3)nanodomains into the layered structure of a typical Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)material,which minimized the Li^(+)/Ni^(2+)cationic disordering,and more importantly,established grain boundaries within the NCM811 matrix,thus providing a three-dimensional diffusion channel for Li ions.Accordingly,an average Li-ion diffusion coefficient(D_(Li+))of the Li_(2)MnO_(3)-integrated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811-I)during charge/discharge was calculated to be approximately 6*10^(-10)cm~2 S^(-1),two times of that in the bare NCM811(3*10^(-10)cm~2 S^(-1)).The capacity delivered by the NCM811-I(154.5 mAh g^(-1))was higher than that of NCM811(141.3 mAh g^(-1))at 2 C,and the capacity retention of NCM811-I increased by 13.6%after100 cycles at 0.1 C and 13.4%after 500 cycles at 1 C compared to NCM811.This work provides a valuable routine to improve the rate capability of Ni-rich cathode materials,which may be applied to other oxide cathodes with sluggish Li-ion transportation.
The different electrocatalytic reactors could be constructed for the electrocatalytic oxidation of 2,2,3,3-tetrafluoro-1-propanol(TFP) with two typical MnO_x/Ti electrodes, i.e.the electrocatalytic membrane reactor(ECMR) with the Ti membrane electrode and the electrocatalytic reactor(ECR) with the traditional Ti plate electrode.For the electro-oxidation of TFP, the conversion with membrane electrode(70.1%) in the ECMR was 3.3 and 1.7 times higher than that of the membrane electrode without permeate flow(40.8%) in the ECMR and the plate electrode(21.5%) in the ECR, respectively.Obviously, the pore structure of membrane and convection-enhanced mass transfer in the ECMR dramatically improved the catalytic activity towards the electro-oxidation of TFP.The specific surface area of porous electrode was 2.22 m^2·g^(-1).The surface area of plate electrode was 2.26 cm^2(1.13 cm^2× 2).In addition, the electrochemical results showed that the mass diffusion coefficient of the MnO_x/Ti membrane electrode(1.80 × 10^(-6) cm^2·s^(-1)) could be increased to 6.87 × 10^(-6) cm^2·s^(-1) at the certain flow rate with pump, confirming the lower resistance of mass transfer due to the convection-enhanced mass transfer during the operation of the ECMR.Hence, the porous structure and convection-enhanced mass transfer would improve the electrochemical property of the membrane electrode and the catalytic performance of the ECMR,which could give guideline for the design and application of the porous electrode and electrochemical reactor.
Hong WangXin WeiYujun ZhangRonghua MaZhen YinJianxin Li
Polymer-derived porous carbon was used as a support of iron and nickel species with an objective to obtain an efficient oxygen reduction reaction(OER)catalyst.The surface features were extensively characterized using X-ray diffraction,X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy.On FeNi-modified carbon the overpotential for OER was very low(280 mV)and comparable to that on noble metal catalyst IrO_(2).The electrochemical properties have been investigated to reveal the difference between the binary alloy-and single metal-doped carbons.This work demonstrates a significant step for the development of low-cost,environmentally-friendly and highly-efficient OER catalysts.
In order to move towards sustainable development, the discovery of energy-efficient and environmentally friendly materials has become increasingly imperative. Covalent organic frameworks(COFs) as emerging designable crystalline porous materials have captured increasing attention for a wide array of clean-energy and environmental applications, attributed to their attractive advantages of low density, high surface area, adjustable and periodic pores, and functional skeletons. This review attempts to highlight the key advancements made in the green synthesis of COFs, processing of COFs, energy and environment-related applications, including gas storage, water treatment, the separation of gas mixture and organic molecules, catalysis, supercapacitors, fuel cell, and rechargeable batteries. Finally, a perspective regarding the remaining challenges and future directions on the synthesis and promising application for green chemical engineering of COFs has also been presented based on current achievements.
P2-Na_(0.67)N_(i0.33)Mn_(0.67)O_(2)is considered as a promising cathode material for sodium-ion battery (SIBs)because of its high capacity and discharge potential.However,its practical use is limited by Na^(+)/vacancy ordering and P2-O2 phase transition.Herein,a Ti^(4+)/F^(-) co-doping strategy is developed to address these issues.The optimal P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) exhibits much enhanced sodium storage performance in the high voltage range of 2.0–4.4 V,including a cycling stability of 77.2%over 300cycles at a rate of 2 C and a high-rate capability of 87.7 m Ah g^(-1) at 6 C.Moreover,the P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) delivers reversible capacities of 82.7 and 128.1 m Ah g^(-1) at-10 and 50℃ at a rate of 2 C,respectively.The capacity retentions over 200 cycles at-10℃ is 94.2%,implying more opportunity for practical application.In-situ X-ray diffraction analysis reveals that both P2-O2 phase transitions and Na^(+)/vacancy ordering is suppressed by Ti^(4+)/F^(-) co-doping,which resulting in fast Na^(+) diffusion and stable phase structure.The hard carbon//P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) full cell exhibits a high energy density of 310.2 Wh kg^(-1) and remarkable cyclability with 82.1%retention after 300 cycles at 1 C in the voltage range of 1.5–4.2 V.These results demonstrate that the co-doping Ti^(4+)/F^(-) is a promising strategy to improve the electrochemical properties of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),providing a facile tactic to develop high performance cathode materials for SIBs.
Exploring new materials to manufacture proton-conducting membranes(PEMs)for fuel cells is highly significant.In this work,we fabricated two robust and highly crystalline porous covalent organic frameworks(COFs)via a stepwise synthesis strategy.The synthesized COF structures are integrated into high-density azo and amino groups,which allow to anchor acids for accelerating proton conduction.Moreover,the COFs exhibit good chemical stability and high hydrophilicity.These features make them potential platforms for proton conduction applications.Upon loaded with H3PO4,the COFs(H3PO4@COFs)deliver a high proton conductivity of 3.15×10‒2 S/cm at 353 K under 95%relative humidity(RH).Furthermore,membrane electrode assemblies are fabricated using H3PO4@COF-26 as the solid electrolyte for a single fuel cell outputting a maximum power density of 18 mW/cm2.
Wearable and portable mobile phones play a critical role in the market, and one of the key technologies is the flexible electrode with high specific capacity and excellent mechanical flexibility. Herein, a wire-in-wire TiO_(2)/C nanofibers (TiO_(2) ww/CN) film is synthesized via electrospinning with selenium as a structural inducer. The interconnected carbon network and unique wire- in-wire nanostructure cannot only improve electronic conductivity and induce effective charge transports, but also bring a superior mechanic flexibility. Ulti-mately, TiO_(2) ww/CN film shows outstanding electrochemical performance as free-standing electrodes in Li/K ion batteries. It shows a discharge capacity as high as 303 mAh g^(−1) at 5 A g^(−1) after 6000 cycles in Li half-cells, and the unique structure is well-reserved after long-term cycling. Moreover, even TiO_(2) has a large diffusion barrier of K^(+), TiO_(2) ww/CN film demonstrates excellent perfor-mance (259 mAh g^(−1) at 0.05 A g^(−1) after 1000 cycles) in K half-cells owing to extraordinary pseudocapacitive contribution. The Li/K full cells consisted of TiO_(2) ww/CN film anode and LiFePO_(4)/Perylene-3,4,9,10-tetracarboxylic dianhydride cathode possess outstanding cycling stability and demonstrate practical application from lighting at least 19 LEDs. It is, therefore, expected that this material will find broad applications in portable and wearable Li/K-ion batteries.
Die SuYi PeiLi LiuZhixiao LiuJunfang LiuMin YangJiaxing WenJing DaiHuiqiu DengGuozhong Cao
