Recent Progress in Emerging Two‑Dimensional Transition Metal Carbides

As a new member in two-dimensional materials family,transition metal carbides(TMCs)have many excellent properties,such as chemical stability,in-plane anisotropy,high conductivity and flexibility,and remarkable energy conversation efficiency,which predispose them for promising applications as transparent electrode,flexible electronics,broadband photodetectors and battery electrodes.However,up to now,their device applications are in the early stage,especially because their controllable synthesis is still a great challenge.This review systematically summarized the state-of-the-art research in this rapidly developing field with particular focus on structure,property,synthesis and applicability of TMCs.Finally,the current challenges and future perspectives are outlined for the application of 2D TMCs.

Two-Dimensional Transition Metal Carbides and Nitrides(MXenes): Synthesis, Properties, and Electrochemical Energy Storage Applications

A family of 2D transition metal carbides and nitrides known as MXenes has received increasing attention since the discovery of Ti3C2 in 2011. To date, about 30 different MXenes with well-defined structures and properties have been synthesized, and many more are theoretically predicted to exist. Due to the numerous assets including excellent mechanical properties, metallic conductivity,unique in-plane anisotropic structure, tunable band gap, and so on, MXenes rapidly positioned themselves at the forefront of the 2D materials world and have found numerous promising applications. Particular interest is devoted to applications in electrochemical energy storage, whereby 2D MXenes work either as electrodes,additives, separators, or hosts. This review summarizes recent advances in the synthesis, fundamental properties and composites of MXene and highlights the state-of-the-art electrochemical performance of MXene-based electrodes/devices.The progresses in the field of supercapacitors and Li-ion batteries, Li-S batteries, Naand other alkali metal ion batteries are reviewed, and current challenges and new opportunities for MXenes in this surging energy storage field are presented. In the focus of interest is the possibility to boost device-level performance, particularly that of rechargeable batteries, which are of utmost importance in future energy technologies. Very recently, the 2019 Nobel Prize in Chemistry was awarded to the inventors of the Li-ion battery. For sure, this will provide an additional stimulation to study fundamental aspects of electrochemical energy storage.

Adhesion between Nonreactive Liquid Metals and Transition Metal Carbides

On the basis of the experimental work of adhesion(W)data,the adhesion between transition metal car- bides and pure liquid metals which do not react with carbides is studied.In view of great scattering of the ex- perimental values of W,a critical analysis of these results is performed.The selected W values for 9 copper/carbide systems and 6 metal/TiC systems are used to discuss the various suggestions concerning the mechanism of adhesion and to evidence the role of the valence electrons of the both carbide and metal on the interactions between metals and carbides.The interactions between a metal and a carbide are essentially metal- lic interactions,resulting from the overlapping of the valence electrons at the metal/carbide interface.

Carbon deficiency introduced plasticity of rock-salt-structured transition metal carbides

High-hardness rock-salt structured transitional metal carbides(TMC)are attracting substantial interest as potential next-generation thermal protection materials.However,the intrinsic brittleness of TMC ceramics impedes their performance in aerodynamically harsh environments.In this work,a promising strategy is proposed to introduce plasticity in TaC–HfC solid solutions by manipulating carbon deficiency.The approach combines density-functional theory(DFT)with experiments and takes Pugh's ratio(k)as the criteria.Depletion of carbon atoms in TaC–HfC solid solutions results in the de-localizing of valence electrons,deviation of spatial modulus along different crystal plane directions,and leading to significant elastic anisotropy.The carbon deficient Ta_(0.8)Hf_(0.2)C_(0.8) is predicted to be a‘softer phase’with reduced modulus and Pugh's ratio(k=0.58).A series of Ta1–xHfxCy(x=0.2 and 0.8,y=0.8,0.9,and 1.0)bulk ceramics are experimentally fabricated by an excessive metal alloying method.Trigonal and hexagonal close-packed structured carbides are derived when the carbon deficiency y decreased to 0.7.The indentation modulus drops from 641.8±14.8 GPa for Ta_(0.8)Hf_(0.2)C_(1.0) to 555.8±9.9 GPa for Ta0.8Hf0.2C0.8.The specific stoichiometric composition of Ta_(0.8)Hf_(0.2)C_(0.8) is experimentally verified to possess both plasticity(k=0.41)and ultra-high nanohardness(41.3±1.3 GPa).

Structural and Electronic Properties of ConC3-/0 and ConC4-/0 （n=1-4） Clusters： Mass-Selected Anion Photoelectron Spectroscopy and Density Functional Theory Calculations

We investigated the structural evolution and elecfronic properties of ConC3-/0 and ConC4-/0 （n=1-4） clusters by using mass-selected photoelectron spectroscopy and density functional theory calculations. The adiabatic and vertical detachment energies of CO1-4C3- and COl-4C4- were obtained from their photoelectron spectra. By comparing the theoretical results with the experimental data, the global minimum structures were determined. The results indicate that the carbon atoms of ConC3-/0 and ConC4-/0 （n=1-4） are separated from each other gradually with increasing number of cobalt atoms but a C2 unit still remains at n=4. It is interesting that the Co2C3- and Co2C4- anions have planar structures whereas the neutral Co2C3 and Co2C4 have linear structures with the Co atoms at two ends. The Co3C3- anion has a planar structure with a Co2C2 four-membered ring and a Co3C four-membered ring sharing a Co-Co bond, while the neutral Co3C3 is a three-dimensional structure with a C2 unit and a C atom connecting to two faces of the Co3 triangle.

Designing of highly selective and high-temperature endurable RWGS heterogeneous catalysts: recent advances and the future directions

Reverse water gas shift（RWGS） reaction can be served as a pivotal stage of transitioning the abundant CO;resource into chemicals or hydrocarbon fuels, which is attractive for the CO;utilization and of eventually significance in enabling a rebuilt ecological system for unconventional fuels. This concept is appealing when the process is considered as a solution for the storage of renewable energy, which may also find a variety of potential end uses for the outer space exploration. However, a big challenge to this issue is the rational design of high temperature endurable RWGS catalysts with desirable CO product selectivity. In this work, we present a comprehensive overview of recent publications on this research topic,mainly focusing on the catalytic performance of RWGS reaction over three major kinds of heterogeneous catalysts, including supported metal catalysts, mixed oxide catalysts and transition metal carbides. The reaction thermodynamic analysis, kinetics and mechanisms are also described in detail. The present review attempts to provide a general guideline about the construction of well-performed heterogeneous catalysts for the RWGS reaction, as well as discussing the challenges and further prospects of this process.

Achieving ultra-broadband electromagnetic wave absorption in high-entropy transition metal carbides (HE TMCs)

Electronic devices pervade everyday life,which has triggered severe electromagnetic(EM)wave pollution.To face this challenge,developing EM wave absorbers with ultra-broadband absorption capacity is critically required.Currently,nano-composite construction has been widely utilized to realize impedance match and broadband absorption.However,complex experimental procedures,limited thermal stability,and interior oxidation resistance are still unneglectable issues.Therefore,it is appealing to realize ultra-broadband EM wave absorption in single-phase materials with good stability.Aiming at this target,two high-entropy transition metal carbides(HE TMCs)including(Zr,Hf,Nb,Ta)C(HE TMC-2)and(Cr,Zr,Hf,Nb,Ta)C(HE TMC-3)are designed and synthesized,of which the microwave absorption performance is investigated in comparison with previously reported(Ti,Zr,Hf,Nb,Ta)C(HE TMC-1).Due to the synergistic effects of dielectric and magnetic losses,HE TMC-2 and HE TMC-3 exhibit better impedance match and wider effective absorption bandwidth(EAB).In specific,the exclusion of Ti element in HE TMC-2 endows it optimal minimum reflection loss(RL_(min))and EAB of−41.7 dB(2.11 mm,10.52 GHz)and 3.5 GHz(at 3.0 mm),respectively.Remarkably,the incorporation of Cr element in HE TMC-3 significantly improves the impedance match,thus realizing EAB of 10.5,9.2,and 13.9 GHz at 2,3,and 4 mm,respectively.The significance of this study lays on realizing ultra-broadband capacity in HE TMC-3(Cr,Zr,Hf,Nb,Ta),demonstrating the effectiveness of high-entropy component design in tailoring the impedance match.

Regulating the formation ability and mechanical properties of high-entropy transition metal carbides by carbon stoichiometry

Tremendous efforts have been dedicated to promote the formation ability of high-entropy transition metal carbides.However,the majority of methods for the synthesis of high-entropy transition metal carbides still face the challenges of high temperature,low efficiency,additional longtime post-treatment and uncontrollable properties.To cope with these challenges,high-entropy transition metal carbides with regulatable carbon stoichiometry(HE TMC)were designed and synthesized,achieving improved ability for single phase solid solutions formation,promoting of sintering and controllable mechanical properties.Two typical composition series,i.e.,easily synthesized(ZrHfTaNb)C(ZHTNC)and difficultly synthesized(Zr_(0.25)Hf_(0.25)Ta_(0.25)Ti_(0.25))C(ZHTTC)are selected to demonstrate the promoting formation ability of single phase solid solutions from carbon stoichiometry deviations.Single phase high-entropy ZHTTC,which has been proven difficult in forming a single phase solid solution,can be prepared with the decrease of C/TM ratio under 2000℃;while the high-entropy ZHTNC,which has been proven easy in forming a single phase solid solution,can be synthesized at lower temperatures with the decrease of C/TM ratio.The synergistic effect of entropy stabilization and reduced chemical bond strength gaining from carbon stoichiometry deviations is responsible for the formation of single phase solid solutions and the promoted sintering of HE TMC.For example,the relative density of bulk(ZrHfTaNb)C(SPS-ZHTNC)increases from 90.98%to 94.25%with decreasing the C/TM atomic ratio from 0.9 to 0.74.More importantly,the room temperature flexural strength,fracture toughness and brittleness index of SPS-ZHTNCcan be tuned in the range of 384 MPa–419 MPa,4.41 MPam–4.73 MPamand 3.679μm–4.083μm,respectively.Thus,the HE TMCprepared by adjusting the ratio of carbon to refractory transition metal oxides have great potential for achieving low temperature synthesis,promoted sintering and tunable properties.

A first-principles investigation on mechanical and metallic properties of titanium carbides under pressure

The titanium carbides are potential candidates to achieve both high hardness and refractory property. We carried out a structural search for titanium carbides at three pressures of 0 GPa, 30 GPa and 50 GPa. A phase diagram of the Ti-C system at 0 K was obtained by elucidating formation enthalpies as a function of compositions, and their mechanical and metallic properties of titanium carbides were investigated sys- tematically. We also discussed the relation of titanium concentration to the both mechanical and metallic properties of titanium carbides. It has been found that the average valence electron density and tractil-ity improved at higher concentrations of titanium, while the degree of covalent bonding directionality decreased. To this effect, the hardness of titanium carbide decreases as the content of titanium increases. Our results indicated that the titanium content significantly affected the metallic properties of the Ti-C system.

The ground-state structure and physical properties of RuC: first-principles calculations

We have extensively explored the ground-state structure of RuC using the particle swarm optimization algorithm for crystal structural prediction. A hexagonal I：t-3m structure has been proposed ms the best candidate, which is energetically more favorable than the previously proposed zinc blend structure. The R-3m-RuC possesses alternative stacking of double hexagonal close-packed Ru atom layers and C atom layers, and it is dynamically stable evidenced by the calculation of phonon dispersion. The calculated large bulk modulus, shear modulus, and elastic constant C44 reveal that it is an ultra-incompressible and hard material. The evidence of strong covalent bonding of Ru C, which plays an important role to form a hard material, is manifested by the partial densities of states analysis.

Ablation behaviour of(Hf-Ta-Zr-Nb)C high entropy carbide ceramic at temperatures above 2100℃

The ablation behaviour of(Hf-Ta-Zr-Nb)C high entropy carbide(HEC4)was studied at temperatures above 2100℃using a plasma flame gun in air.The microstructures,phase and chemical compositions of the HEC4 samples were investigated after ablation.The mass ablation rate of the HEC4 samples increased with increasing ablation time from 0.21 mg cm^(−2)s^(−1)for 60 s to 0.45 mg cm^(−2)s^(−1)for 120 s.Com-pared to the mono-and binary carbides with commonly decreased mass and thickness after ablation,the HEC4 samples with the increased mass and thickness after ablation showed good resistance to mechan-ical scouring at such high temperatures and an oxidation controlled ablation mechanism.The ablation processes mainly include the oxidation of the carbide,the phase separation of the oxides,the melting of oxides,and the diffusion of oxygen.A composition gradient in the oxide layer was detected due to the different melting temperatures of the different oxides;Nb-Ta rich oxides formed at the front surface melted and became enriched at the edge of the samples,and the Zr-Hf rich oxides were enriched in the centre of the samples.The oxide layer with complex compositions and phase distributions acted as an effective ablation barrier.

Rational design of 3D porous niobium carbide MXene/rGO hybrid aerogels as promising anode for potassium-ion batteries with ultrahigh rate capability

An effective method is designed to construct three-dimensional(3D)Nb_(2)C/reduced graphene oxide(rGO)hybrid aerogels through a low-temperature graphene oxide(GO)-assisted hydrothermal self-assembly followed by freeze-drying and annealing.The intimately coupled Nb_(2)C/rGO hybrid aerogel combines the advantages of large specific surface area and rich 3D interconnected porous structure of aerogel as well as high conductivity and low potassium diffusion energy barrier of Nb_(2)C,which not only effectively prevents the self-restacking of Nb2C nanosheets to allow more active sites exposed and accommodate the volume change during the charge/discharge process,but also increases the accessibility of electrolyte and promotes the rapid transfer of ions/electrons.As a result,Nb_(2)C/rGO-2 as the anode of potassium ion batteries(KIBs)delivers a large reversible specific capacity(301.7 mAh·g^(−1)after 500 cycles at 2.0 A·g^(−1)),an ultrahigh rate capability(155.5 mAh·g^(−1)at 20 A·g^(−1)),and an excellent long-term large-current cycle stability(198.8 mAh·g^(−1)after 1,000 cycles at 10 A·g^(−1),with a retention of 83.3%).Such a high-level electrochemical performance,especially the ultrahigh rate capability,is the best among transition metal carbides and nitride(MXene)-based materials reported so far for KIBs.The diffusion kinetics of K+is investigated thoroughly,and the synergetic charge–discharge mechanism and the structure–performance relationship of Nb_(2)C/rGO are revealed explicitly.The present work provides a good strategy to solve the self-restacking problem of two-dimensional materials and also enlarges the potential applications of MXenes.

Vertically mounting molybdenum disulfide nanosheets on dimolybdenum carbide nanomeshes enables efficient hydrogen evolution

Designing hierarchical heterostructure to optimize the adsorption of hydrogen intermediate(H*)is impressive for hydrogen evolution reaction(HER)catalysis.Herein,we show that vertically mounting two-dimensional(2D)layered molybdenum disulfide(MoS_(2))nanosheets on 2D nonlayered dimolybdenum carbide(Mo_(2)C)nanomeshes to form a hierarchical heterostructure largely accelerates the HER kinetics in acidic electrolyte due to the weakening adsorption strength of H*on 2D Mo_(2)C nanomeshes.Our hierarchical MoS2/Mo2C heterostructure therefore gives a decrease of overpotential for up to 500 mV at-10 mA·cm^(-2)and an almost 200-fold higher kinetics current density compared with the pristine Mo2C nanomeshes and maintains robust stability with a small drop of overpotential for only 16 mV upon 5,000 cycles.We further rationalize this finding by theoretical calculations and find an optimized adsorption free energy of H*,identifying that the MoS_(2)featuring strong H*desorption plays a key role in weakening the strong binding of Mo_(2)C with H*and therefore improves the intrinsic HER activity on active C sites of Mo_(2)C.This present finding shines the light on the rational design of heterostructured catalysts with synergistic geometry.

V_(8)C_(7)/C稳定的超细Ru纳米颗粒用于全pH下的析氢反应

The development of cost-effective electrocatalysts with high efficiency and long durability for hydrogen evolution reaction(HER)remains a great challenge in the field of water splitting.Herein,we design an ultrafine and highly dispersed Ru nanoparticles stabilized on porous V_(8)C_(7)/C matrix via pyrolysis of the metal-organic frameworks V-BDC(BDC:1,4-benzenedicarboxylate).The obtained Ru-V_(8)C_(7)/C composite exhibits excellent HER performance in all p H ranges.At the overpotential of 40 mV,its mass activity is about 1.9,4.1 and 9.4 times higher than that of commercial Pt/C in acidic,neutral and alkaline media,respectively.Meanwhile,Ru-V_(8)C_(7)/C shows the remarkably high stability in all p H ranges which,in particular,can maintain the current density of 10 m A cm^(-2)for over 150 h in 1.0 mol L^(-1)phosphate buffer saline(PBS).This outstanding HER performance can be attributed to the high intrinsic activity of Ru species and their strong interface interactions to the V_(8)C_(7)/C substrate.The synergistic effect of abundant active sites on the surface and the formed Ru-C-V units at the interface promotes the adsorption of reaction intermediates and the release of active sites,contributing the fast HER kinetics.This work provides a reference for developing versatile and robust HER catalysts by surface and interface regulation for pH tolerance.

Recent advances in crystal phase induced surface-enhanced Raman scattering

Surface-enhanced Raman scattering(SERS)spectroscopy has emerged as a powerful analytical technique for detecting and identifying trace chemical and biological molecules.In this review,we present an indepth discussion of recent advances in the field of crystal phase manipulation to achieve exceptional SERS performance.Focusing on transition metal dichalcogenides,(hydr)oxides,and carbides as exemplary materials,we illustrate the pivotal role of crystal phase regulation in enhancing SERS signals.By exploring the correlation between crystal phases and SERS responses,we uncover the underlying principles behind these strategies,thereby shedding light on their potential for future SERS applications.By addressing the current challenges and limitations,we also propose the prospects of the crystal phase strategy to facilitate the development of cutting-edge SERS-based sensing technologies.

Thermal transports in the MXenes family:Opportunities and challenges

The carbides and nitrides of transition metals known as“MXenes”refer to a fast-growing family of two-dimensional materials discovered in 2011.Thanks to their unique nanolayer structure,superior electrical,mechanical,and thermal properties,MXenes have shown great potential in addressing the critical overheating issues that jeopardize the performance,stability,and lifetime of high-energy-density components in modern devices such as microprocessors,integrated circuits,and capacitors,etc.The outstanding intrinsic thermal conductivity of MXenes has been proved by experimental and theoretical research.Numerous MXenes-enabled high thermal conductivity composites incorporated with polymer matrix have also been reported and widely used as thermal management materials.Considering the booming heat dissipation demands,MXenes-enabled thermal management material is an extremely valuable and scalable option for modern electronics industries.However,the fundamental thermal transport mechanisms behind the MXenes family remain unclear.The MXene thermal conductivity disparities between the theoretical prediction and experimental results are still significant.To better understand the thermal conduction in MXenes and provide more insights for engineering high-performance MXene thermal management materials,in this article,we summarize recent progress on thermal conductive MXenes.The essential factors that affect MXenes intrinsic thermal conductivities are tackled,selected MXenes-polymer composites are highlighted,and prospects and challenges are also discussed.

Sequentially bridged MXene platelets for strong high‐temperature EM‐IR bi‐stealth sheets

Combination of flexible multifunctional stealth technology properties such as electromagnetic(EM)and infrared(IR)stealth is crucial to the development of aerospace,military,and electronic fields,but the synthesis technology still has a significant challenge.Herein,we have successfully designed and synthesized highly flexible MXene@cellulose lamellae/borate ion(MXCB)sheets with strong high‐temperature EM‐IR bi‐stealth through sequential bridging of hydrogen and covalent bonds.The resultant MXCB sheets display high conductivity and good mechanical features such as flexibility,stretchability,fatigue resistance,and ultrasonic damage.MXCB sheets have a high tensile strength of 795 MPa.Furthermore,MXCB sheets with different thicknesses indicate exceptional high‐temperature thermal‐camouflage characteristics.This reduces the radiation temperature of the target object(>300°C)to 100°C.The conductivity of MXCB sheet with 3μm thickness is 6108 S/cm and the EM interference(EMI)shielding value is 39.74 dB.The normalized surface‐specific EMI SE absolute shielding effectiveness(SSE/t)is as high as 39312.78 dB·cm2/g,which remained 99.39%even after 10,000 times repeated folding.These multifunctional ultrathin MXCB sheets can be arranged by vacuum‐assisted induction to develop EM‐IR bi‐stealth sheet.

Electromagnetic wave absorbing properties of TMCs(TM=Ti,Zr,Hf,Nb and Ta)and high entropy(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C

Electromagnetic wave(EMW)absorbing materials play a vital role in modern communication and information processing technologies to inhibit information leakage and prevent possible damages to environment and human bodies.Currently,most of EMW absorbing materials are either composites of two or more phases or in the form of nanosheets,nanowires or nanofibers in order to enhance the EMW absorption performance through dielectric loss,magnetic loss and dielectric/magnetic loss coupling.However,the combination of complex shapes/multi phases and nanosizes may compound the difficulties of materials processing,composition and interfaces control as well as performance maintenance during service.Thus,searching for single phase materials with good stability and superior EMW absorbing properties is appealing.To achieve this goal,the EMW absorbing properties of transition metal carbides TMCs(TM=Ti,Zr,Hf,Nb and Ta)and high entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C which belong to ultrahigh temperature ceramics,were investigated in this work.Due to the good electrical conductivity and splitting of d orbitals into lower energy t2glevel and higher energy eglevel in TMC6octahedral arrangement,TMCs(TM=Ti,Zr,Hf,Nb and Ta)exhibit good EMW absorbing properties.Especially,Hf C and Ta C exhibit superior EMW absorbing properties.The minimum reflection loss(RLmin)value of Hf C is-55.8 d B at 6.0 GHz with the thickness of 3.8 mm and the effective absorption bandwidth(E_(AB))is 6.0 GHz from 12.0 to 18.0 GHz at thickness of 1.9 mm;the RL_(minvalue)of Ta C reaches-41.1 d B at 16.2 GHz with a thickness of 2.0 mm and the EABis 6.1 GHz with a thickness of 2.2 mm.Intriguingly,the electromagnetic parameters,i.e.,complex permittivity and permeability are tunable by forming single phase solid solution or high entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C.The R_(Lminvalue)of high entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C is-38.5 d B at 9.5 GHz with the thickness of 1.9 mm,and the EABis 2.3 GHz(from 11.3 to 13.6 GHz)at thickness of 1.5 mm.The significance of this work is that it opens a new window to design single phase high performance EMW absorbing materials by dielectric/magnetic loss coupling through tuning the conductivity and crystal field splitting energy of d orbitals of transition metals in carbides,nitrides and possibly borides.

Recent advance in electromagnetic shielding of MXenes

As a new type of two-dimensional material,MXene’s unique layered structure,outstanding electrical conductivity,low density,tunable surface chemistry,and solution processability make it receive extensive attention in various fields,especially for the lightweight shielding mate rials since the report on electromagnetic interference(EMI) shielding of 2D Ti3 C2 Tx in 2016.In this review,the progress on the MXe nes material including their synthetic strategies,prope rties and EMI application is highlighted.First,the recent advance on the different synthesis methods and properties of MXene is summarized.According to their intrinsic characteristics,the application of MXene in EMI fields is then discussed.Finally,the challenges and perspective on the future development of MXene in low-cost preparation and practical application are proposed.

Low thermal conductivity and high porosity ZrC and HfC ceramics prepared by in-situ reduction reaction/partial sintering method for ultrahigh temperature applications

Porous ultra-high temperature ceramics(UHTCs) are potential candidates as high-temperature thermal insulation materials. However, high thermal conductivity is the main obstacle to the application of porous UHTCs. In order to address this problem, herein, a new method combining in-situ reaction and partial sintering has been developed for preparing porous Zr C and Hf C with low conductivity. In this process, porous Zr C and Hf C are directly obtained from ZrO2/C and HfO2/C green bodies without adding any pore-forming agents. The release of reaction gas can not only increase the porosity but also block the shrinkage. The asprepared porous Zr C and Hf C exhibit homogeneous porous microstructure with grain sizes in the range of 300–600 nm and 200–500 nm, high porosity of 68.74% and 77.82%, low room temperature thermal conductivity of 1.12 and 1.01 W·m-1 K-1, and compressive strength of 8.28 and 5.51 MPa, respectively.These features render porous Zr C and Hf C promising as light-weight thermal insulation materials for ultrahigh temperature applications. Furthermore, the feasibility of this method has been demonstrated and porous Nb C, Ta C as well as Ti C have been prepared by this method.