Multiscale confinement nitridation in molybdenum carbide for efficient hydrogen production

The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.

Mesoporous molybdenum carbide for greatly enhanced hydrogen evolution at high current density and its mechanism studies

Currently the catalysis of hydrogen evolution reaction(HER)is mainly focused on the inherent electrocatalytic activity at relatively lower current densities while scarce at high current densities.Nevertheless,the latter is highly demanding in efficient mass-production of hydrogen.A SiO_(2) nanospheres template-synthesis is used to prepare mesoporous molybdenum carbide nanocrystals-embedded nitrogen-doped carbon foams(mp-Mo_(2)C/NC).The material shows much more excellent catalytic activity than the non-etched Mo_(2)C/NC toward hydrogen evolution reaction(HER)in acidic medium.More interestingly mp-Mo_(2)C/NC still has larger overpotential than Pt/C at lower current densities,but possess remarkably smaller overpotential than the latter at higher current densities for much better electrocatalytic performance.An approach is developed to investigate the electrode kinetics by Tafel plots,especially with eliminating the diffusion effect,indicating that Pt/C and mp-Mo_(2)C/NC display different reaction mechanisms.At low current densities the former presents reversible reaction,while the latter shows mixed electrochemical polarization/reversible electrode process.In the region of higher current densities,the former becomes totally gas-diffusion controlled with large overpotential,while the latter can still retain an electrode polarization process for much lower overpotential at the same current density.Result endorses that the meso-porously structured mp-Mo_(2)C/NC plays a critical role in avoiding gas diffusion control-resulting large overpotential at high current densities.This work holds great potential for an inexpensive catalyst better than Pt/C in practical applications of mass-production hydrogen at high current densities,while clearly shedding fundamental lights on designs of rational HER catalysts for the uses at high current densities.

Thermodynamic study and methanothermal temperature-programmed reaction synthesis of molybdenum carbide

Nanostructured molybdenum carbide （Mo2C） was successfully prepared from molybdenum trioxide （MoO3） using methanothermal temperature-programmed reaction. Thermodynamic analysis indicated that in presence of methane, the formation of Mo2C from MoO3 occurs through the path of MoO3 → MoO2→ Mo2C. The carburized MoO3 was characterized using X-ray diffraction （XRD）, CHNS/O analysis, Brunauer-Emmett-Teller （BET） analysis, and field-emission scanning electron microscopy （FESEM）. At final carburization temperatures of 700 and 800℃ and at methane contents ranging from 5vol% to 20vol%, Mo2C was the only solid product observed in the XRD patterns. The re- suits indicated that the effect of methane content on the formation of the carbide phase is substantial compared with the effect of carburization time. Elemental analysis showed that at a final temperature of 700℃, the carbon content of carburized MoO3 is very close to the theoretical carbon mass percentage in Mo2C. At higher carburization temperatures, excess carbon was deposited onto the surface of Mo2C. High-surface-area Mo2C was obtained at extremely low heating rates; this high-surface-area material is a potential electrocatalyst.

Molybdenum carbide clusters for thermal conversion of CO2 to CO via reverse water-gas shift reaction

Molybdenum carbides are highly active for CO2 conversion to CO via the reverse water-gas shift(RWGS)reaction, however the large grain size up to micrometers renders its relatively lower active sites utilization efficiency while generating CH4 as a by-product. In this work, a homogeneously dispersed molybdenum carbide hybrid catalyst with sub-nanosized cluster(the average size as small as 0.5 nm) is prepared via a facile carbothermal treatment for highly selective CO2-CO reduction. The partially disordered Mo2C clusters are characterized by synchrotron high-resolution XRD and atomic resolution HAADF-STEM analysis, for which the source cause of the disorder is pinpointed by XAFS analysis to be the nitrogen intercalants from the carbonaceous precursor. The partially disordered Mo2C clusters show a RWGS rate as high as 184.4 μmol gMo2C-1s-1 at 400 ℃ with a superior selectivity toward CO(> 99.5%). This work 2 highlights a facile strategy for fabricating highly dispersed and partially disordered Mo2C clusters at a sub-nano size with beneficial N-doping for delivering high catalytic activity and operational stability.

Coupled cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes supported on nickel foam as a binder-free electrode for overall water splitting

In an attempt to develop low-cost,non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media,cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C3N4 as the carbon source on a 3D porous nickel foam substrate.Benefiting from the optimized electronic structure and enhanced mass and charge transport,as well as the 3D conducting pathway,MoxCoy@N-CNSs/CNTs shows superior performance towards both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in an alkaline medium.The optimal electrocatalyst is Mo2Co1@N-CNSs/CNTs,which reveals a current density of 10 mA cm^-2 at the low overpotentials of 99 mV and 300 mV for the HER and OER,respectively,and a relatively low cell voltage(1.63 V)for the overall water electrolysis.The method of optimizing the composition and nanostructure of a material provides a new avenue for the development and utilization of high-performance electrocatalysts.

Preparation of ultramicro molybdenum carbide powders and study on wear properties of their coating

Using specially designed mechanochemical ball-mill equipment, ultramicro molybdenum carbide （MoC） powders were prepared by high-energy ball milling from pure molybdenum powders in civil coal gas atmosphere at room temperature. The structure and the particle size of the powders were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and Transmission Electron micros-copy （TEM）. The results showed that after milling for 30 h, the MoC powders of hexagonal structure were obtained, and their average parti-cle size was around 100 nm. It was found that chemisorption of CO in coal gas onto the fresh molybdenum surfaces created by milling was the predominant processes during the solid-gas reaction, and the energy input due to the introduction of highly dense grain boundaries and lattice defects provided the activation energy for the transition from Mo-C chemisorption to MoC. A coating was formed on the 40Cr steel base using plasma spray by mixing Ni60 alloy powders and ultramicro MoC powders of 5 wt.%, 10 wt.%, and 15 wt.%, respectively. Coat-ing abrasion tests under the condition of dry-grinding, 2 h wear time, and 300 N load showed that the wear resistance property of the coating added with ultramicro MoC powders could be improved greatly, and the wear resistance property of the coating increased with the increase of ultramicro MoC content. The wear mechanisms of ultramicro MoC coating is mainly plough wear and flaking wear assisted. In the abra-sion process, the evenly distributed ultramicro MoC particles play a dispersion strengthening and self-lubricating role in the coating.

XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation

The X-ray photoelectron spectroscopy （XPS） was used to investigate the surface characteristic of potassium-promoted or un-promoted both β-Mo2C and α-MoC1-x pretreated by syngas at different temperatures,and the promotional effect of potassium on the catalytic performance was also studied.XPS results revealed that the content of surface Mo and its valence distribution between β-Mo2C and α-MoC1-x were quite different.Promoted by potassium,the remarkable changes were observed for surface composition and valence of Mo distribution over β-Mo2C.Potassium had strong electronic effect on β-Mo2C,which led to a higher Mo4＋ content.On the contrary,potassium had little electronic effect on α-MoC1-x,and K-Mo interaction was weak.Therefore,Mo0 and Mo2＋ became the dominant species on the catalyst surface,and the Mo4＋ content showed almost no increase as the pretreatment temperature enhanced.In terms of catalytic performance of molybdenum carbides,the increase in Mo0 most likely explained the increase in hydrocarbon selectivity,yet Mo4＋ might be responsible for the alcohols synthesis.

Design and modulation principles of molybdenum carbide-based materials for green hydrogen evolution

The green production of hydrogen from electrocatalytic water splitting is an important base and promising direction for the future of the large-scale application of hydrogen energy.The key of green hydrogen evolution depends on the development of low-cost and highly active electrocatalysts.Molybdenum carbides(MoxC),as a typical of earth-abundant transition-metal material,have accumulated great attention due to their low cost,earth abundance,electrical conductivity,similar d-band state to Pt,and regulated morphology/electronic structures.In this paper,recent researches focusing on MoxC for efficient HER in a wide pH range are summarized from respects of modulation of unique morphology,electronic structure,and electrode interface step by step.Briefly,modulation of morphology influence the apparent activity of catalyst,modulation of electronic structure of active sites by heteroatom doping and designing heterointerface boost intrinsic HER kinetics,and modulation of electrode interface via hybridization of MoxC structures with carbon materials can ensure the fast electron transfer and boost the activity.Besides the above methods discussed,perspective and challenges of designing MoxC as the substitute of Pt-based electrocatalyst for practical hydrogen generation in a wide pH range are pointed out.

Molybdenum carbide as catalyst in biomass derivatives conversion

The present energy dilemma in conjunction with the adverse environmental impacts caused by fossil fuel combustion motivates researchers to seek for new renewable energy with minimal CO_(2)footprint.As a practice pathway,it is of significance to produce biofuel and platform chemicals from sustainable biomass resources.However,the research and development of high-efficiency catalysts remain one key scientific challenge.Among the catalysts developed,transition metal carbides,especially molybdenum carbide,show promising performances on biomass-based conversion.Significant efforts have been made in past few decades on tuning the structure and electronic property of molybdenum carbide via controlling particle size and morphology,metal and nonmetal doping and vacancies,etc.The review summarizes recent developments of molybdenum carbide as catalysts in converting biomass into fuel,mainly focused on the preparation methods,the structure-dependent effects and the electronic modulation.The controllable selective cleavage of C-C,C-O and C-H bonds over modified molybdenum carbides that has been demonstrated in the conversion of biomass feedstocks is then highlighted.In addition,the possible deactivation mechanisms of molybdenum carbide are also presented in the review.This review provides systematic and fundamental information for the further design and development of molybdenum carbide for the conversion of biomass resources.

Single-step thermal carburization synthesis of supported molybdenum carbides from molybdenum-containing methyl-silica

A novel synthesis route to obtain highly dispersed molybdenum carbides in porous silica is described. The synthesis was carried out by a single-step heat treatment of molybdenum-containing and methyl-modified silica （Mo-M-SiO2） in argon atmosphere at 973 K. Mo-M-SiO2 precursor was facilely obtained via a one-pot synthesis route, using （NH4）6Mo7O24 4H2O （AHM） as molybdenum sources and polymethylhydrosiloxane （PMHS） as silica sources at the initial synthetic step. The optimal C/Mo molar ratio in reaction system for complete carburization of molybdenum species was 7. The carburization process of molybdenum species followed a nontopotactic route involving a MoO2 intermediate phase, which was evidenced by XRD, N2 adsorption-desorption and in situ XPS. Formation mechanism of Mo-M-SiO2 precursor was also proposed by observation of the reaction between AHM and PMHS with TEM. Furthermore, by adding TEOS into silica sources and adjusting TEOS/PMHS mass ratio, crystal phase of molybdenum carbides transferred from β-Mo2C to α-MoC1-x, and SiO2 structure changed from microporous to micro/mesoporous. Catalytic performances of samples were tested using CO hydrogenation as a probe reaction. The supported molybdenum carbides exhibited high selectivity for higher alcohol synthesis compared with bulk β-Mo2C and α-MoC1-x.

Investigation on the Performance of Supported Molybdenum Carbide for the Partial Oxidation of Methane

The performance of supported and unsupported molybdenum carbide for thepartial oxidation of methane (POM) to syngas was investigated. An evaluation of the catalystsindicates that bulk molybdenum carbide has a higher methane conversion during the initial stage buta lower selectivity to CO and H_2/CO ratio in the products. The rapid deactivation of the catalystis also a significant problem. However, the supported molybdenum carbide catalyst shows a muchhigher methane conversion, increased selectivity and significantly improved catalytic stability. Thecharacterization by XRD and BET specific area measurements depict an improved dispersion ofmolybdenum carbide when using alumina as a carrier. The bulk or the supported molybdenum carbideexists in the β-MO_2C phase, while it is transformed into molybdenum dioxide postcatalysis which isan important cause of molybdenum carbide deactivation.

Synergistic Effect of Nitrogen/Phosphorus Co-Doping and Molybdenum Carbide Induced Electron Redistribution of Carbon Layer to Boost Hydrogen Evolution Reaction

The development of highly efficient non-precious-metal-based electrocatalysts for the hydrogen evolution reaction is imperative for promoting the large-scale application of electrochemical water splitting.Herein,nitrogen/phosphorus co-doped carbon nanorods encapsulated Mo_(2)C nanoparticles(Mo_(2)C@PNc)have been prepared by pre-phosphating treatment in combination of the coordination with polydopamine and the subsequent pyrolysis.The phosphating temperature has a significant effect on the content of phosphorus within the resultant Mo_(2)C@PNC,and the optimal catalyst delivers superior HER activity with the low overpotential of 104 mV at a current density of 10 mAcm^(-2) and good stability for 8 h,which has been theoretically demonstrated to originate from the synergistic effect between P doping and Mo_(2)C induced electron redistribution of nitrogen-doped carbon layer.

Interfacial engineering of atomic platinum-doped molybdenum carbide quantum dots for high-rate and stable hydrogen evolution reaction in proton exchange membrane water electrolysis

Platinum(Pt)-based electrocatalysts remain the only practical cathode catalysts for proton exchange membrane water electrolysis(PEMWE),due to their excellent catalytic activity for acidic hydrogen evolution reaction(HER),but are greatly limited by their low reserves and high cost.Here,we report an interfacial engineering strategy to obtain a promising low-Pt loading catalyst with atomically Pt-doped molybdenum carbide quantum dots decorated on conductive porous carbon(Pt-MoCx@C)for high-rate and stable HER in PEMWE.Benefiting from the strong interfacial interaction between Pt atoms and the ultra-small MoCx quantum dots substrate,the Pt-MoCx catalyst exhibits a high mass activity of 8.00 A·mgPt−1,5.6 times higher than that of commercial 20 wt.%Pt/C catalyst.Moreover,the strong interfacial coupling of Pt and MoCx substrate greatly improves the HER stability of the Pt-MoCx catalyst.Density functional theory studies further confirm the strong metal-support interaction on Pt-MoCx,the critical role of MoCx substrate in the stabilization of surface Pt atoms,as well as activation of MoCx substrate by Pt atoms for improving HER durability and activity.The optimized Pt-MoCx@C catalyst demonstrates>2000 h stability under a water-splitting current of 1000 mA·cm^(−2)when applied to the cathode of a PEM water electrolyzer,suggesting the potential for practical applications.

Two-dimensional molybdenum carbide(MXene)as an efficient nanoadditive for achieving superlubricity under ultrahigh pressure

In this study,a robust macroscale liquid superlubricity with a coefficient of friction of 0.004 was achieved by introducing molybdenum carbide(Mo_(2)CT_(x))MXene nanoparticles as lubricating additives in a lithium hexafluorophosphate-based ionic liquid at Si_(3)N_(4)-sapphire interfaces.The maximal contact pressure in the superlubricity state could reach 1.42 GPa,which far exceeds the limit of the superlubricity regime in previous studies.The results indicate that a composite tribofilm(mainly containing molybdenum oxide and phosphorus oxide)that formed at the interface by a tribochemical reaction contributed to the excellent antiwear performance.Furthermore,the extremely low shear strength of the tribofilm and the interlayers of Mo_(2)CT_(x)MXene contributed to the superlubricity.This work demonstrates the promising potential of Mo_(2)CT_(x)MXene in improving superlubricity properties,which could accelerate the application of superlubricity in mechanical systems.

Effects of Carbide Formation in Graphene Growth

Besides carbon solubility, the carbide formation possibility is another important factor to differentiate various substrate materials in graphene growth. A recent experiment indicates that the formation of transition metal carbides （TMCs） can suppress carbon precipitation. In this study, Mo2C, a representative of TMCs, is used to study the effects of carbide formation in graphene growth from first principles. Carbon diffusion in Mo2C bulk turns out to be very difficult and it becomes much easier on the Mo2C（001） surface. Therefore, carbon precipitation suppression and graphene growth can be realized simultaneously. A direction depended diffusion behavior is observed on the Mo2C（101） surface, which makes it less favorable for graphene growth compared to the （001） surface.

Self-catalyzed formation of strongly interconnected multiphase molybdenum-based composites for efficient hydrogen evolution

Molybdenum carbide(MoxC)with variable phase structure possesses flexible hydrogen-binding energy(HBE),which is a promising hydrogen evolution reaction(HER)catalyst.Herein,a hybrid multiphase MoxC freestanding film coupled with Co3Mo(CM/MoxC@NC)is synthesized through the electrospinning method supplemented by the heteroatom incorporation.CM/MoxC@NC surpasses its pure phase counterparts and exhibits remarkable catalytic activity at 114mV to deliver a current density of 10mA cm^(−2) in acid,which is among the first-rate level performance reported for MoxC-based catalysts.The subsequent ex situ and in situ characterizations reveal a phase transition mechanism based on self-catalysis that CoOx depletes the coordinated C ofα-MoC via the interaction,which realizes the assembly of weak HBEα-MoC and strong HBEβ-Mo2C,and the enhanced utilization of active materials as well.The multiple structures with optimal HBE are in favor of the stepwise reactions of HER,as the study of the correlation between HBE and phase structure revealed.This study discloses the underlying phase transition mechanism and highlights the HBE–structure relationship that should be considered for catalyst design.

Synergistic Effect of Dual-Doped Carbon on MO_(2)C Nanocrystals Facilitates Alkaline Hydrogen Evolution

Molybdenum carbide(MO_(2)C)materials are promising electrocatalysts with potential applications in hydrogen evolution reaction(HER)due to low cost and Pt-like electronic structures.Nevertheless,their HER activity is usually hindered by the strong hydrogen binding energy.Moreover,the lack of water-cleaving site's makes it difficult for the catalysts to work in alkaline solutions.Here,we designed and synthesized a B and N dual-doped carbon layer that encapsulated on MO_(2)C nanocrystals(MO_(2)C@BNC)for accelerating HER under alkaline condition.The electronic interactions between the MO_(2)C nanocrystals and the multiple-doped carbon layer endow a near-zero H adsorption Gibbs free energy on the defective C atoms over the carbon shell.Meanwhile,the introduced B atoms afford optimal H_2O adsorption sites for the water-cleaving step.Accordingly,the dual-doped MO_(2)C catalyst with synergistic effect of non-metal sites delivers superior HER performances of a low overpotential(99 mV@10 mA cm^(-2))and a small Tafel slope(58.1 mV dec^(-1))in 1 M KOH solution.Furthermore,it presents a remarkable activity that outperforming the commercial 10%Pt/C catalyst at large current density,demonstrating its applicability in industrial water splitting.This study provides a reasonable design strategy towards noble-metal-free HER catalysts with high activity.

Construction of Mo/Mo_(2)C@C modified ZnIn_(2)S_(4)Schottky junctions for efficient photo-thermal assisted hydrogen evolution

Photocatalytic water splitting on noble metal-free photocatalysts for H_(2) generation is a promising but challenging approach to realize solar-to-chemical energy conversion.In this study,Mo/Mo_(2)C nanoparticles anchored carbon layer(Mo/Mo_(2)C@C)was obtained by a one-step in-situ phase transition approach and developed for the first time as a photothermal cocatalyst to enhance the activity of ZnIn_(2)S_(4)photocatalyst.Mo/Mo_(2)C@C nanosheet exhibits strong absorption in the full spectrum region and excellent photo-thermal conversion ability,which generates heat to improve the reaction temperature and accelerate the reaction kinetics.Moreover,metallic Mo/Mo_(2)C@C couples with ZnIn_(2)S_(4)to form ZnIn_(2)S_(4)-Mo/Mo_(2)C@C Schottky junction(denoted as ZMM),which prevents the electrons back transfer and restrains the charge recombination.In addition,conductive carbon with strong interfacial interaction serves as a fast charge transport bridge.Consequently,the optimized ZMM-0.2 junction exhibits an H2 evolution rate of 1031.07μmol g^(-1)h^-(1),which is 41 and 4.3 times higher than bare ZnIn_(2)S_(4)and ZnIn_(2)S_(4)-Mo2C,respectively.By designing novel photothermal cocatalysts,our work will provide a new guidance for designing efficient photocatalysts.

Synergistically boosting the elementary reactions over multiheterogeneous ordered macroporous Mo2C/NC-Ru for highly efficient alkaline hydrogen evolution

Simultaneously enhancing the reaction kinetics,mass transport,and gas release during alkaline hydrogen evolution reaction(HER)is critical to minimizing the reaction polarization resistance,but remains a big challenge.Through rational design of a hierarchical multiheterogeneous three-dimensionally(3D)ordered macroporous Mo_(2)C-embedded nitrogen-doped carbon with ultrafine Ru nanoclusters anchored on its surface(OMS Mo_(2)C/NC-Ru),we realize both electronic and morphologic engineering of the catalyst to maximize the electrocatalysis performance.The formed Ru-NC heterostructure shows regulative electronic states and optimized adsorption energy with the intermediate H*,and the Mo_(2)C-NC heterostructure accelerates the Volmer reaction due to the strong water dissociation ability as confirmed by theoretical calculations.Consequently,superior HER activity in alkaline solution with an extremely low overpotential of 15.5 mV at 10 mAcm^(−2)with the mass activity more than 17 times higher than that of the benchmark Pt/C,an ultrasmall Tafel slope of 22.7 mV dec−1,and excellent electrocatalytic durability were achieved,attributing to the enhanced mass transport and favorable gas release process endowed from the unique OMS Mo_(2)C/NC-Ru structure.By oxidizing OMS Mo_(2)C/NC-Ru into OMS MoO_(3)-RuO_(2)catalyst,it can also be applied as efficient oxygen evolution electrocatalyst,enabling the construction of a quasi-symmetric electrolyzer for overall water splitting.Such a device's performance surpassed the state-of-the-art Pt/C||RuO2 electrolyzer.This study provides instructive guidance for designing 3D-ordered macroporous multicomponent catalysts for efficient catalytic applications.

Study on reduction of MoS_2 powders with activated carbon to produce Mo_2C under vacuum conditions

A method of preparing Mo2C via vacuum carbothermic reduction of MoS2 in the temperature range of 1350–1550°C was proposed. The effects of MoS2-to-C molar ratio（a, a = 1：1, 1：1.5, and 1：2.5） and reaction temperature（1350 to 1550°C） on the reaction were studied in detail. The phase transition, morphological evolution, and residual sulfur content of the products were analyzed by X-ray diffraction, field-emission scanning electron microscopy, and carbon–sulfur analysis, respectively. The results showed that the complete decomposition of MoS2 under vacuum is difficult, whereas activated carbon can react with MoS2 under vacuum to generate Mo2C. Meanwhile, higher temperatures and the addition of more carbon accelerated the rate of carbothermic reduction reaction and further decreased the residual sulfur content. From the experimental results, the optimum molar ratio α was concluded to be 1：1.5.