Recent advances in nickel-based catalysts in eCO_(2)RR for carbon neutrality

The excessive use of nonrenewable energy has brought about serious greenhouse effect.Converting CO_(2) into high-value-added chemicals is undoubtedly the best choice to solve energy problems.Due to the excellent cost-effectiveness and dramatic catalytic performance,nickel-based catalysts have been considered as the most promising candidates for the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR).In this work,the electrocatalytic reduction mechanism of CO_(2) over Ni-based materials is reviewed.The strategies to improve the eCO_(2)RR performance are emphasized.Moreover,the research on Ni-based materials for syngas generation is briefly summarized.Finally,the prospects of nickel-based materials in the eCO_(2)RR are provided with the hope of improving transition-metal-based electrocatalysts for eCO_(2)RR in the future.

A review on electrocatalytic CO_(2) conversion via C-C and C-N coupling

Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.

Hydrogen evolution reaction activity enhancement from active site turnover mechanism

Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-doped Ni_(2)P catalyst as a research model and found that the introduction of heterogeneous Co reconstructed the charge distribution around the P site,which effectively enhanced the hydrogen evolution reaction(HER)activity of the pure Ni_(2)P.Based on in-situ Raman real-time monitoring technology,we monitored for the first time that Co doping triggered a switch of the active site(from the original Co-active site to the P-active site),which promoted the adsorption of H_(2)O to enhance the HER activity.The density functional theory(DFT)calculations indicated that the P site of Co-Ni_(2)P expressed the highest activity and the Ni site of pure Ni_(2)P expressed the highest activity,which further confirms the in-situ Raman monitoring results.The active site turnover mechanism discovered in this study will undoubtedly provide more rational and targeted ideas for future catalyst design.

Vertical 3D Nanostructures Boost Efficient Hydrogen Production Coupled with Glycerol Oxidation Under Alkaline Conditions

Hydrogen production from electrolytic water is an important sustainable technology to realize renewable energy conversion and carbon neutrality.However,it is limited by the high overpotential of oxygen evolution reaction(OER)at the anode.To reduce the operating voltage of electrolyzer,herein thermodynamically favorable glycerol oxidation reaction(GOR)is proposed to replace the OER.Moreover,vertical Ni O flakes and NiMoNH nanopillars are developed to boost the reaction kinetics of anodic GOR and cathodic hydrogen evolution,respectively.Meanwhile,excluding the explosion risk of mixed H_2/O_(2),a cheap organic membrane is used to replace the expensive anion exchange membrane in the electrolyzer.Impressively,the electrolyzer delivers a remarkable reduction of operation voltage by 280 mV,and exhibits good long-term stability.This work provides a new paradigm of hydrogen production with low cost and good feasibility.

Ion–Electron Coupling Enables Ionic Thermoelectric Material with New Operation Mode and High Energy Density

Ionic thermoelectrics(i-TE) possesses great potential in powering distributed electronics because it can generate thermopower up to tens of millivolts per Kelvin. However,as ions cannot enter external circuit, the utilization of i-TE is currently based on capacitive charge/discharge, which results in discontinuous working mode and low energy density. Here,we introduce an ion–electron thermoelectric synergistic(IETS)effect by utilizing an ion–electron conductor. Electrons/holes can drift under the electric field generated by thermodiffusion of ions, thus converting the ionic current into electrical current that can pass through the external circuit. Due to the IETS effect, i-TE is able to operate continuously for over 3000 min.Moreover, our i-TE exhibits a thermopower of 32.7 mV K^(-1) and an energy density of 553.9 J m^(-2), which is more than 6.9 times of the highest reported value. Consequently, direct powering of electronics is achieved with i-TE. This work provides a novel strategy for the design of high-performance i-TE materials.

Anode Interfacial Issues in Solid-State Li Batteries:Mechanistic Understanding and Mitigating Strategies

All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significant progress has been made on improving the ionic conductivity of SEs,the degradation and instability of Li metal/inorganic SE interfaces have become the critical challenges that limit the coulombic efficiency,power performance,and cycling stability of ASSLBs.Understanding the mechanisms of complex/dynamic interfacial phenomena is of great importance in addressing these issues.Herein,recent studies on identifying,understanding,and solving interfacial issues on anode side in ASSLBs are comprehensively reviewed.Typical issues at Li metal/SE interface include Li dendrite growth/propagation,SE cracking,physical contact loss,and electrochemical reactions,which lead to high interfacial resistance and cell failure.The causes of these issues relating to the chemical,physical,and mechanical properties of Li metal and SEs are systematically discussed.Furthermore,effective mitigating strategies are summarized and their effects on suppressing interfacial reactions,improving interfacial Li-ion transport,maintaining interfacial contact,and stabilizing Li plating/stripping are highlighted.The in-depth mechanistic understanding of interfacial issues and complete investigations on current solutions provide foundations and guidance for future research and development to realize practical application of high-performance ASSLB.

MOF-based quasi-solid-state electrolyte for long-life Al-Se battery

Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.

Model of Surface Texture for Honed Gear Considering Motion Path and Geometrical Shape of Abrasive Particle

Gear power-honing is mainly applied to finish small and medium-sized automotive gears,especially in new energy vehicles.The distinctive curved surface texture greatly improves the noise emission and service life of honed gears.The surface texture for honed gear considering the motion path and geometrical shape of abrasive particles has not been investigated.In this paper,the kinematics of the gear honing process is analyzed,and the machining marks produced by the abrasive particles of honing wheel scratching abrasive particles against the workpiece gear are calculated.The tooth surface roughness is modeled considering abrasive particle shapes and material plastic pile-ups.This results in a mathematical model that characterizes the structure of the tooth surface and the orientation of the machining marks.Experiments were used to verify the model,with a maximum relative error of less than 10%when abrasive particles are spherical.Based on this model,the effects of process parameters on the speeds of discrete points on the tooth flank,orientations of machining marks and roughness are discussed.The results show that the shaft angle between the workpiece gear and the honing wheel and the speed of the honing wheel is the main process parameters affecting the surface texture.This research proposes a surface texture model for honed gear,which can provide a theoretical basis for optimizing process parameters for gear power-honing.

Creation of Triple Hierarchical Micro-Meso-Macroporous N-doped Carbon Shells with Hollow Cores Toward the Electrocatalytic Oxygen Reduction Reaction

A series of triple hierarchical micro-mesomacroporous N-doped carbon shells with hollow cores have been successfully prepared via etching N-doped hollow carbon spheres with CO_2 at high temperatures.The surface areas, total pore volumes and microporepercentages of the CO_2-activated samples evidently increase with increasing activation temperature from 800 to950 °C, while the N contents show a contrary trend from7.6 to 3.8 at%. The pyridinic and graphitic nitrogen groups are dominant among various N-containing groups in the samples. The 950 °C-activated sample(CANHCS-950) has the largest surface area(2072 m^2 g^(-1)), pore volume(1.96 cm^3 g^(-1)), hierarchical micro-mesopore distributions(1.2, 2.6 and 6.2 nm), hollow macropore cores(*91 nm)and highest relative content of pyridinic and graphitic N groups. This triple micro-meso-macropore system could synergistically enhance the activity because macropores could store up the reactant, mesopores could reduce the transport resistance of the reactants to the active sites, and micropores could be in favor of the accumulation of ions.Therefore, the CANHCS-950 with optimized structure shows the optimal and comparable oxygen reduction reaction(ORR) activity but superior methanol tolerance and long-term durability to commercial Pt/C with a 4 e--dominant transfer pathway in alkaline media. These excellent properties in combination with good stability and recyclability make CANHCSs among the most promising metal-free ORR electrocatalysts reported so far in practical applications.

One-pot hydrothermal fabrication of α-Fe_2O_3@C nanocomposites for electrochemical energy storage

A facile hydrothermal method was developed for the preparation of Fe_2O_3@C nanocomposites using FeCl_3·6H_2O as iron source and glucose as carbon source under alkaline condition. The morphology and structure of the as-prepared product were identified by transmission electron microscopy(TEM), high resolution transmission electron microscopy(HRTEM), field-emission scanning electron microscopy(FESEM),X-ray diffraction(XRD), Raman spectroscopy, Fourier Transform infrared spectroscopy(FTIR), and thermogravimetric analysis(TGA). The as-prepare α-Fe_2O_3@C nanocomposites were employed for supercapacitor electrode material. The synergistic combination of carbon electrical double-layer capacitance and α-Fe_2O_3 pseudo-capacitance established such nanocomposites as versatile platform for high performance supercapacitors. The synthesis method developed here is expected to obtain other metal oxide/carbon composite.

Recent Advances on Boosting the Cell Voltage of Aqueous Supercapacitors

Due to its ultra-fast charge/discharge rate,long cyclic life span,and environmental benignity,aqueous supercapacitor(SC)is considered as a proper nextgeneration energy storage device.Unfortunately,limited by undesirable water electrolysis and unreasonable electrode potential range,aqueous SC normally generates a narrow cell voltage,resulting in a low energy density.To address such challenge,enormous efforts have been made to construct high-voltage aqueous SCs.Despite these achievements,the systematic reviews about this field are still rare.To fill this knowledge gap,this review summarizes the recent advances about boosting the cell voltage of aqueous SCs.From the viewpoint of electrode,doping alkali cations,modulating the electrode mass ratio,and optimizing the surface charge density are regarded as three effective pathways to achieve this goal.However,adjusting the appropriate pH level,introducing redox mediators,and constructing“water-in-salt”electrolyte are other three universal routes from the electrolyte aspect.Furthermore,it is also effective to obtain the high-voltage aqueous SCs through asymmetric design,such as designing asymmetric SCs.The confronting challenges and future development tendency towards the high-voltage aqueous SCs are further discussed.

Prediction of coal structure using particle size characteristics of coalbed methane well cuttings

Severely deformed coal seams barely deliver satisfactory gas production. This research was undertaken to develop a new method to predict the positions of deformed coals for a horizontal CBM well. Firstly, the drilling cuttings of different structure coals were collected from a coal mine and compared. In light of the varying cuttings characteristics for different structure coals, the coal structure of the horizontally drilled coal seam was predicted. And the feasibility of this prediction method was discussed. The result shows that exogenetic fractures have an important influence on the deformation of coal seams. The hardness coefficient of coal decreases with the deformation degree in the order of primary structural, cataclastic and fragmented coal. And the expanding-ratio of gas drainage holes and the average particle size of cuttings increase with the increase of the deformation degree. The particle size distribution of coal cuttings for the three types of coals is distinctive from each other. Based on the particle size distribution of cuttings from X-2 well in a coal seam, six sections of fragmented coal which are unsuitable for perforating are predicted. This method may benefit the optimization of perforation and fracturing of a horizontal CBM well in the study area.

Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction

A series of N-doped carbon materials(NCs)were synthesized by using biomass citric acid and dicyandiamide as renewable raw materials via a facile onestep pyrolysis method. The characterization of microstructural features shows that the NCs samples are composed of few-layered graphene-like nanoflakes with controlled in situ N doping, which is attributed to the confined pyrolysis of citric acid within the interlayers of the dicyandiamide-derived g-C_3N_4 with high nitrogen contents. Evidently, the pore volumes of the NCs increased with the increasing content of dicyandiamide in the precursor. Among these samples, the NCs nanoflakes prepared with the citric acid/dicyandiamide mass ratio of 1:6, NC-6,show the highest N content of ~6.2 at%, in which pyridinic and graphitic N groups are predominant. Compared to the commercial Pt/C catalyst, the as-prepared NC-6 exhibits a small negative shift of ~66 mV at the half-wave potential, demonstrating excellent electrocatalytic activity in the oxygen reduction reaction. Moreover, NC-6 also shows better long-term stability and resistance to methanol crossover compared to Pt/C. The efficient and stable performance are attributed to the graphene-like microstructure and high content of pyridinic and graphitic doped nitrogen in the sample, which creates more active sites as well as facilitating charge transfer due to the close four-electron reaction pathway. The superior electrocatalytic activity coupled with the facile synthetic method presents a new pathway to cost-effective electrocatalysts for practical fuel cells or metal–air batteries.

Modeling investigation of geometric size effect on pervaporation dehydration through scaled-up hollow fiber NaA zeolite membranes

A mass transfer model in consideration of multi-layer resistances through NaA zeolite membrane and lumen pressure drop in the permeate side was developed to describe pervaporation dehydration through scaled-up hollow fiber supported NaA zeolite membrane. It was found that the transfer resistance in the lumen of the permeate side is strongly related with geometric size of hollow fiber zeolite membrane, which could not he neglected. The effect of geometric size on pervaporation dehydration could be more significant under higher vacuum pressure in the permeate side. The transfer resistance in the lumen increases with the hollow fiber length but decreases with lumen diameter. The geometric structure could be optimized in terms of the ratio of lumen diameter to membrane length. A critical value of d1/L （Rc） to achieve high permeation flux was empirically correlated with extraction pressure in the permeate side. Typically, for a hollow fiber supported NaA zeolite membrane with length of 0.40 m, the lumen diameter should be larger than 2.0 mm under the extraction pressure of 1500 Pa.

Mesoporous Ternary Nitrides of Earth?Abundant Metals as Oxygen Evolution Electrocatalyst

As sustainable energy becomes a major concern for modern society,renewable and clean energy systems need highly active,stable,and low-cost catalysts for the oxygen evolution reaction(OER).Mesoporous materials offer an attractive route for generating efficient electrocatalysts with high mass transport capabilities.Herein,we report an efficient hard templating pathway to design and synthesize three-dimensional(3-D)mesoporous ternary nickel iron nitride(Ni3FeN).The as-synthesized electrocatalyst shows good OER performance in an alkaline solution with low overpotential(259 mV)and a small Tafel slope(54 mV dec?1),giving superior performance to IrO2 and RuO2 catalysts.The highly active contact area,the hierarchical porosity,and the synergistic effect of bimetal atoms contributed to the improved electrocatalytic performance toward OER.In a practical rechargeable Zn–air battery,mesoporous Ni3FeN is also shown to deliver a lower charging voltage and longer lifetime than RuO2.This work opens up a new promising approach to synthesize active OER electrocatalysts for energy-related devices.

Hierarchical N-Doped Porous Carbons for Zn–Air Batteries and Supercapacitors

Nitrogen-doped carbon materials with a large specific surface area,high conductivity,and adjustable microstructures have many prospects for energy-related applications.This is especially true for N-doped nanocarbons used in the electrocatalytic oxygen reduction reaction(ORR)and supercapacitors.Here,we report a low-cost,environmentally friendly,large-scale mechanochemical method of preparing N-doped porous carbons(NPCs)with hierarchical micro-mesopores and a large surface area via ball-milling polymerization followed by pyrolysis.The optimized NPC prepared at 1000°C(NPC-1000)offers excellent ORR activity with an onset potential(Eonset)and half-wave potential(E1/2)of 0.9 and 0.82 V,respectively(vs.a reversible hydrogen electrode),which are only approximately 30 mV lower than that of Pt/C.The rechargeable Zn–air battery assembled using NPC-1000 and the NiFe-layered double hydroxide as bifunctional ORR and oxygen evolution reaction electrodes offered superior cycling stability and comparable discharge performance to RuO2 and Pt/C.Moreover,the supercapacitor electrode equipped with NPC prepared at 800℃ exhibited a high specific capacity(431 F g^−1 at 10 mV s^−1),outstanding rate,performance,and excellent cycling stability in an aqueous 6-M KOH solution.This work demonstrates the potential of the mechanochemical preparation method of porous carbons,which are important for energy conversion and storage.

One stone two birds:Vanadium doping as dual roles in self-reduced Pt clusters and accelerated water splitting

Integrating active Pt clusters into transition-metal oxides with water-dissociation ability is effective to prepare a bifunctional electrocatalyst for water splitting in alkaline.However,the additional utilization of a reductant and/or the operation at the elevating temperature causes the over-growth and agglomeration of Pt clusters,thus losing the high catalytic performance.Herein,we report that V dopant not only favors self-reducing Pt clusters on Ni Fe layered double hydroxide(LDH)(Pt/NiFeV)at room temperature,but also regulates interfacial charge redistribution to enhance the water-splitting performance.Experimental and theoretical studies reveal that V dopant into Ni Fe LDH triggers more electrons to transfer to adjacent Fe atoms,thus leading to a higher reducing ability compared to that without V-doping.When used as water-splitting electrocatalyst,V doping promotes electron loss of Pt clusters in Pt/Ni Fe V,optimizing the free energy of hydrogen adsorption and proton recombination kinetics at the cathode.Meanwhile,it also moves the d-band center of Ni away from the Fermi level to optimize the adsorption of*OH intermediates and facilitate the desorption of oxygen molecules at the anode.Thereby,Pt/Ni Fe V exhibits much higher bifunctional performance than V-free Pt/Ni Fe LDH toward both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).This work can spark inspiration of designing other bifunctional electrocatalysts for energy conversion and storage.

LPR-Trie: A Fast IPv6 Routing Lookup Algorithm with Virtual Nodes

The number of IPv6 routes in todays backbone routers has grown rapidly,which has put tremendous pressure on route lookup and storage.Based on the analysis of IPv6 address prefix length and distribution characteristics,this paper proposes an IPv6 route lookup architecture called LPR-Trie.The core idea of the algorithm is to utilize more spaces and accelerate routing lookup.Moreover,we put forward the concept of virtual nodes,and leverage the link between virtual nodes and ordinary nodes to accelerate routing lookup.We provide the longest prefix routing entry(LPR)calculation algorithm to achieve the longest prefix match.The experimental results show that the virtual node mechanism increases the search speed up to 244%,and the virtual nodes have better stability by setting an appropriate keep-alive time according to the characteristics of actual traffic.This paper shows that our design improves the routing lookup speed and have better memory utilization.

高吸附电化学纤维传感器用于实时、准确检测颅内一氧化氮

电化学一氧化氮传感器能够实时监测颅内一氧化氮浓度,对于了解大脑中一氧化氮的功能至关重要.然而,在大脑中使用的传统刚性传感电极面临着灵敏度低和植入后神经炎症引起一氧化氮浓度异常的问题.在这里,我们报道了一种结合物理和化学吸附能力、具有高灵敏度和准确性的电化学一氧化氮传感器.其对一氧化氮的物理和化学吸附能力分别来自于电极的高比表面积和丰富的羧基官能团.此外,柔软的电极可以与脑组织的力学性能相匹配,实现了一个高度适应的电极/组织界面.由此设计的颅内一氧化氮传感器表现出迄今为止所报道文献中最高的灵敏度,为3245 pA nmol^(-1)L,检测限为0.1 nmol L^(-1).电极在植入后未观察到显著的炎症反应以及过量的一氧化氮表达,提高了检测的准确性.该传感器成功捕捉了大脑中的一氧化氮波动,并实现了对多个脑区的同时检测,促进了对大脑中一氧化氮生理病理作用的研究.

Glycerol Electrooxidation to Value-Added C_(1)-C_(3)Chemicals:Mechanism Analyses,Influencing Factors,Catalytic Regulation,and Paired Valorization

Glycerol,as a byproduct of biodiesel production,can be used to produce a variety of high-value C_(1),C_(2),and C_(3)chemicals by electrocatalytic glycerol oxidation reaction(EGOR).Further coupling EGOR with CO_(2)reduction reaction(CO_(2)RR)or hydrogen evolution reaction(HER)in paired electrolyzers is increasingly attractive due to the reduced input energy for the simultaneous formation of value-added products on both sides of the cell.This review article introduces the main reaction path of EGOR and the influencing factors of the reaction conditions of EGOR.The catalysts for the highly selective formation of glyceric acid,lactic acid,tartaric acid(TA),or formic acid(FA)from EGOR are highlighted.The latest research progress on design strategies of catalysts required for these reactions was reviewed.Subsequently,the paired electrolyzers coupling EGOR with HER or electrocatalytic CO_(2)RR were evaluated.Finally,the challenges and prospects in the field of EGOR are pointed out to move forward with the future development of glycerol electrocatalysis.