Crystalline Phase Engineering to Modulate the Interfacial Interaction of the Ruthenium/Molybdenum Carbide for Acidic Hydrogen Evolution.

Ruthenium (Ru) is an ideal substitute to commercial Pt/C for the acidic hydrogen evolution reaction (HER), but it still suffers from undesirable activity due to the strong adsorption free energy of H* (ΔGH*). Herein, we propose crystalline phase engineering by loading Ru clusters on precisely prepared cubic and hexagonal molybdenum carbide (α-MoC/ß-Mo2C) supports to modulate the interfacial interactions and achieve high HER activity. Advanced spectroscopies demonstrate that Ru on ß-Mo2C shows a lower valence state and withdraws more electrons from the support than that of Ru on α-MoC, indicative of a strong interfacial interaction. Density functional theory reveals that the ΔGH* of Ru/ß-Mo2C approaches 0 eV, illuminating an enhancement mechanism at the Ru/ß-Mo2C interface. The resultant Ru/ß-Mo2C exhibits an encouraging performance in a proton exchange membrane water electrolyzer with a low cell voltage (1.58 V@ 1.0 A cm-2) and long stability (500 h@ 1.0 A cm-2).

Ultra-Dispersed α-MoC1-x Embedded in a Plum-Like N-Doped Carbon Framework as a Synergistic Adsorption-Electrocatalysis Interlayer for High-Performance Li-S Batteries.

The shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) severely hinder the scalable application of lithium-sulfurr (Li-S) batteries. Herein, the highly dispersed α-phase molybdenum carbide nano-crystallites embedded in a porous nitrogen-doped carbon framework (α-MoC1-x @NCF) are developed via a simple metal-organic frameworks (MOFs) assisted strategy and proposed as the multifunctional separator interlayer for Li-S batteries. The inlaid MoC1-x nanocrystals and in situ doped nitrogen atoms provide a strong chemisorption and outstanding electrocatalytic conversion toward LiPSs, whereas the unique plum-like carbon framework with hierarchical porosity enables fast electron/Li+ transfer and can physically suppress LiPSs shuttling. Benefiting from the synergistic trapping-catalyzing effect of the MoC1-x @NCF interlayer toward LiPSs, the assembled Li-S battery achieves high discharge capacities (1588.1 mAh g-1 at 0.1 C), impressive rate capability (655.8 mAh g-1 at 4.0 C) and ultra-stable lifespan (a low capacity decay of 0.059% per cycle over 650 cycles at 1.0 C). Even at an elevated sulfur loading (6.0 mg cm-2 ) and lean electrolyte (E/S is ≈5.8 µL mg-1 ), the battery can still achieve a superb areal capacity of 5.2 mAh cm-2 . This work affords an effective design strategy for the construction of muti-functional interlayer in advanced Li-S batteries.

Interfacial Synergy in Mo2C/MoC Heterostructure Promoting Sequential Polysulfide Conversion in High-Performance Lithium-Sulfur Battery.

A rational design of sulfur host is the key to conquering the"polysulfide shuttle effects" by accelerating the polysulfide conversion. Since the process involves solid-liquid-solid multistep phase transitions, purposely-engineered heterostructure catalysts with various active regions for catalyzing conversion steps correspondingly are beneficial to promote the overall conversion process. However, the functionalities of the materials surface and interface in heterostructure catalysts remain unclear. In this work, an Mo2C/MoC catalyst with abundant Mo2C surface-interface-MoC surface tri-active-region is developed by in situ converting the MoZn-metal organic framework. The experimental and simulation studies demonstrate the interface can catch long-chain polysulfides and promote their conversion. Instead, the Mo2C and MoC tend to accommodate the short-chain polysulfide and accelerate their conversion and the Li2S dissociation. Benefitting from the high catalytic ability, the Li-S battery assembled with the Mo2C/MoC-S cathode shows more discrete redox reactions and delivers a high initial capacity of 1603.6 mAh g-1 at 1 C charging-discharging rate, which is over twofolds of the one assembled using individual hosts, and 80.4% capacity can be maintained after 1000 cycles at 3 C rate. This work has demonstrated a novel synergy between the interface and material surface, which will help the future design of high-performance Li-S batteries.

Anchoring Ultrafine ß-Mo2C Clusters Inside Porous Co-NC Using MOFs for Electric-Powered Coproduction of Valuable Chemicals.

Electroredox of organics provides a promising and green approach to producing value-added chemicals. However, it remains a grand challenge to achieve high selectivity of desired products simultaneously at two electrodes, especially for non-isoelectronic transfer reactions. Here a porous heterostructure of Mo2C@Co-NC is successfully fabricated, where subnanometre ß-Mo2C clusters (<1 nm, ≈10 wt%) are confined inside porous Co, N-doped carbon using metalorganic frameworks. It is found that Co species not only promote the formation of ß-Mo2C but also can prevent it from oxidation by constructing the heterojunctions. As noted, the heterostructure achieves >96% yield and 92% Faradaic efficiency (FE) for aldehydes in anodic alcohol oxidation, as well as >99.9% yield and 96% FE for amines in cathodal nitrocompounds reduction in 1.0 M KOH. Precise control of the reaction kinetics of two half-reactions by the electronic interaction between ß-Mo2C and Co is a crucial adjective. Density functional theory (DFT) gives in-depth mechanistic insight into the high aldehyde selectivity. The work guides authors to reveal the electrooxidation nature of Mo2C at a subnanometer level. It is anticipated that the strategy will provide new insights into the design of highly effective bifunctional electrocatalysts for the coproduction of more complex fine chemicals.

Tailoring Pseudo-Graphitic Domain by Molybdenum Modification to Boost Sodium Storage Capacity and Durability for Hard Carbon.

Hard carbon (HC) stands out as the most prospective anode for sodium-ion batteries (SIBs) with significant potential for commercial applications. However, some long-standing and intractable obstacles, like low first coulombic efficiency (ICE), poor rate capability, storage capacity, and cycling stability, have severely hindered the conversion process from laboratory to commercialization. The above-mentioned issues are closely related to Na+ transfer kinetics, surface chemistry, and internal pseudo-graphitic carbon content. Herein, constructing molybdenum-modified hard carbon solid spheres (Mo2C/HC-5.0), both the ion transfer kinetics, surface chemistry, and internal pseudo-graphitic carbon content are comprehensively improved. Specifically, Mo2C/HC-5.0 with higher pseudo-graphitic carbon content provides a large number of active sites and a more stable layer structure, resulting in improved sodium storage capacity, rate performance, and cycling stability. Moreover, the lower defect density and specific surface area of Mo2C/HC-5.0 further enhance ICE and sodium storage capacity. Consequently, the Mo2C/HC-5.0 anode achieves a high capacity of 410.7 mA h g-1 and an ICE of 83.9% at 50 mA g-1. Furthermore, the material exhibits exceptional rate capability and cycling stability, maintaining a capacity of 202.8 mA h g-1 at 2 A g-1 and 214.9 mA h g-1 after 800 cycles at 1 A g-1.

Theoretical Insight into the Special Synergy of Bimetallic Site in Co/MoC Catalyst to Promote N2 -to-NH3 Conversion.

The catalytic mechanisms of nitrogen reduction reaction (NRR) on the pristine and Co/α-MoC(001) surfaces were explored by density functional theory calculations. The results show that the preferred pathway is that a direct N≡N cleavage occurs first, followed by continuous hydrogenations. The production of second NH3 molecule is identified as the rate-limiting step on both systems with kinetic barriers of 1.5 and 2.0 eV, respectively, indicating that N2 -to-NH3 transformation on bimetallic surface is more likely to occur. The two components of the bimetallic center play different roles during NRR process, in which Co atom does not directly participate in the binding of intermediates, but primarily serves as a reservoir of H atoms. This special synergy makes Co/α-MoC(001) have superior activity for ammonia synthesis. The introduction of Co not only facilitates N2 dissociation, but also accelerates the migration of H atom due to the antibonding characteristic of Co-H bond. This study offers a facile strategy for the rational design and development of efficient catalysts for ammonia synthesis and other reactions involving the hydrogenation processes.

High yield and wide lateral size growth of α-Mo2C: exploring the boundaries of CVD growth of bare MXene analogues.

Synthesis of Mo2C bare MXenes, without surface terminations groups, via chemical vapor deposition (CVD) on metal foils is scientifically a very intriguing crystal growth process, and there are still challenges and limited fundamental understanding to overcome to obtain high yield and wide crystal size lateral growth. Achieving large area coverage via direct growth is scientifically vital to utilize the full potential of their unique properties in different applications. In this study, we sought to expand the boundaries of the current CVD growth approach for Mo2C MXenes and gain insights into the possibilities and limitations of large area growth, with a particular focus on controlling Mo concentration. We report a facile modification of their typical CVD growth protocol and show its influence on the Mo2C synthesis, with growth times spanning up to 3 h. Specifically, prior to initiating the CVD growth process, we introduced a holding step in temperature at 1095 °C. This proved to be beneficial in increasing the Mo concentration on the liquid Cu growth surface. We achieved an average Mo2C crystals coverage of approximately 50% of the growth substrate area, increased tendency of coalescence and merging of individual flakes, and lateral flake sizes up to 170µm wide. To gain deeper understanding into their CVD growth behavior, we conducted a systematic investigation of the effect of several factors, including (i) a holding step time on Mo diffusion rate through molten Cu, (ii) the Cu foil thickness over the Mo foil, and (iii) the CVD growth time. Phase, chemical and microstructural characterization by x-ray diffraction, x-ray photon spectroscopy, SEM and scanning/transmission electron microscopy revealed that the grown crystals are single phaseα-Mo2C. Furthermore, insights gained from this study sheds light on crucial factors and inherent limitations that are essential to consider and may help guide future research progress in CVD growth of bare MXenes.

In-Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water-Gas Shift Reaction.

In situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water-gas shift (RWGS) reaction. Surface oxygen atoms in various Mo-based catalysts are removed in H2-containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt-dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal -1 ⋅ h-1 at 600 °C has been achieved over in situ carbonized H-intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.

Room Temperature Ion Beam Synthesis of Ultra-Fine Molybdenum Carbide Nanoparticles: Toward a Scalable Fabrication Route for Earth-Abundant Electrodes.

Molybdenum carbides are promising low-cost electrocatalysts for electrolyzers, fuel cells, and batteries. However, synthesis of ultrafine, phase-pure carbide nanoparticles (diameter < 5 nm) with large surface areas remains challenging due to uncontrollable agglomeration that occurs during traditional high temperature syntheses. This work presents a scalable, physical approach to synthesize molybdenum carbide nanoparticles at room temperature by ion implantation. By tuning the implantation conditions, various molybdenum carbide phases, stoichiometries, and nanoparticle sizes can be accessed. For instance, molybdenum ion implantation into glassy carbon at 30 keV energy and to a fluence of 9 × 1016 at cm-2 yields a surface η-Mo3 C2 with a particle diameter of (10 ± 1) nm. Molybdenum implantation into glassy carbon at 60 keV to a fluence of 6 × 1016 at cm-2 yields a buried layer of ultrafine γ'-MoC/η-MoC nanoparticles. Carbon ion implantation at 20 keV into a molybdenum thin film produces a 40 nm thick layer primarily composed of ß-Mo2 C. The formation of nanoparticles in each molybdenum carbide phase is explained based on the Mo-C phase diagram and Monte-Carlo simulations of ion-solid interactions invoking the thermal spike model. The approaches presented are widely applicable for synthesis of other transition metal carbide nanoparticles as well.

Multiphase Molybdenum Carbide Doped Carbon Hollow Sphere Engineering: The Superiority of Unique Double-Shell Structure in Microwave Absorption.

In order to achieve excellent electromagnetic wave (EMW) absorption properties, the microstructure design and component control of the absorber are critical. In this study, three different structures made of Mo2 C/C hollow spheres are prepared and their microwave absorption behavior is investigated. The Mo2 C/C double-shell hollow spheres consisting of an outer thin shell and an inner rough thick shell with multiple EMW loss mechanisms exhibit good microwave absorption properties. In order to further improve the microwave absorption properties, MoC1-x /C double-shell hollow spheres with different crystalline phases of molybdenum carbide are prepared to further optimize the EMW loss capability of the materials. Finally, MoC1-x /C double-shell hollow spheres with α-phase molybdenum carbide have the best microwave absorption properties. When the filling is 20 wt.%, the minimum reflection loss at 1.8 mm is -50.55 dB and the effective absorption bandwidth at 2 mm is 5.36 GHz, which is expected to be a microwave absorber with the characteristics of "thin, light, wide, and strong".

Surface Stretching Enables Highly Disordered Graphitic Domains for Ultrahigh Rate Sodium Storage.

Hard carbons (HCs) with high sloping capacity are considered as the leading candidate anode for sodium-ion batteries (SIBs); nevertheless, achieving basically complete slope-dominated behavior with high rate capability is still a big challenge. Herein, the synthesis of mesoporous carbon nanospheres with highly disordered graphitic domains and MoC nanodots modification via a surface stretching strategy is reported. The MoOx surface coordination layer inhibits the graphitization process at high temperature, thus creating short and wide graphite domains. Meanwhile, the in situ formed MoC nanodots can greatly promote the conductivity of highly disordered carbon. Consequently, MoC@MCNs exhibit an outstanding rate capacity (125 mAh g-1 at 50 A g-1 ). The "adsorption-filling" mechanism combined with excellent kinetics is also studied based on the short-range graphitic domains to reveal the enhanced slope-dominated capacity. The insight in this work encourages the design of HC anodes with dominated slope capacity toward high-performance SIBs.

Ruthenium and Iron Co-doped Molybdenum Carbide as a Stable Hydrogen Evolution Electrocatalyst in Harsh Electrolyte.

Electrocatalytic water splitting is one of the most commercially valuable pathways of hydrogen production especially combined with renewable electricity; however, efficient and durable electrocatalysts are urgently needed to reduce electric energy consumption. Here, we reported a Ru and Fe co-doped Mo2 C on nitrogen doped carbon via a controllable two-step method, which can be used for efficient and enduring hydrogen evolution reaction. At 10, 100 and 200 mA cm-2 in acidic electrolyte, the resultant Ru-Fe/Mo2 C@NC delivered low overpotentials of 31, 78 and 103 mV, respectively, which are comparable to that of the commercial Pt/C (20 wt %). At an applied current density of 100 mA cm-2 , stable hydrogen production was conducted for 120 h without obvious degradation. In alkaline media, Ru-Fe/Mo2 C@NC can also deliver a current density of 100 mA cm-2 for more than 100 h. Furthermore, the Ru-Fe/Mo2 C@NC electrocatalyst was used as cathode in an anion exchange membrane water electrolyzer under industrial environments for robust hydrogen production. The characterization and electrochemical results prove the synergism effects between Ru, Fe dopants and Mo2 C for promoting hydrogen evolution activity. This work would pave a new avenue to fabricate low-cost, high-performance hydrogen evolution electrocatalysts for industrial water electrolyzers.

Sustainable Production of Molybdenum Carbide (MXene) from Fruit Wastes for Improved Solar Evaporation.

Freshwater production using solar-driven interfacial evaporation is regarded as a green and sustainable strategy. The biggest barrier to practical deployment of solar desalination, however, continues to be the lack of options for renewable materials. Herein, we present a facile two-step carbonization approach that is sustainable for developing innovative two-dimensional (2D) molybdenum carbide (Mo2 C) materials derived from carbonized fruit wastes. The resultant 2D Mo2 C photothermal layer has an efficient water evaporation rate of 1.52 kg m-2 h-1 with a photothermal conversion efficiency of 94 % under one sun irradiation, which is among the best reported values so far. The broad solar absorption band, high specific surface area (555.1 m2 g-1 ) with large micro- and meso porosity, of the Mo2 C photothermal layer are responsible for these outstanding results. The conversion of food wastes into valuable products, in this case MXene, can potentially inspire greener developments of advanced materials for solar water evaporator.

Green fabrication of ultrafine N-MoxC/CoP hybrids for boosting electrocatalytic water reduction.

Developing non-noble-metal electrocatalysts for hydrogen evolution reactions with high activity and stability is the key issue in green hydrogen generation based on electrolytic water splitting. It has been recognized that the stacking of large CoP particles limits the intrinsic activity of as-synthesized CoP catalyst for hydrogen evolution reaction. In the present study, N-MoxC/CoP-0.5 with excellent electrocatalytic activity for hydrogen evolution reaction was prepared using N-MoxC as decoration. A reasonable overpotential of 106 mV (at 10 mA cm-2) and a Tafel slope of 59 mV dec-1in 1.0 M KOH solution was achieved with N-MoxC/CoP-0.5 electrocatalyst, which exhibits superior activity even after working for 37 h. Uniformly distributed ultrafine nanoclusters of the N-MoxC/CoP-0.5 hybrids could provide sufficient interfaces for enhanced charge transfer. The effective capacity of the hydrogen evolution reaction could be preserved in the complex, and the enlarged electrocatalytic surface area could be expected to offer more active sites for the reaction.

Superconductivity enhancement in phase-engineered molybdenum carbide/disulfide vertical heterostructures.

Stacking layers of atomically thin transition-metal carbides and two-dimensional (2D) semiconducting transition-metal dichalcogenides, could lead to nontrivial superconductivity and other unprecedented phenomena yet to be studied. In this work, superconducting α-phase thin molybdenum carbide flakes were first synthesized, and a subsequent sulfurization treatment induced the formation of vertical heterolayer systems consisting of different phases of molybdenum carbide-ranging from α to γ' and γ phases-in conjunction with molybdenum sulfide layers. These transition-metal carbide/disulfide heterostructures exhibited critical superconducting temperatures as high as 6 K, higher than that of the starting single-phased α-Mo2C (4 K). We analyzed possible interface configurations to explain the observed moiré patterns resulting from the vertical heterostacks. Our density-functional theory (DFT) calculations indicate that epitaxial strain and moiré patterns lead to a higher interfacial density of states, which favors superconductivity. Such engineered heterostructures might allow the coupling of superconductivity to the topologically nontrivial surface states featured by transition-metal carbide phases composing these heterostructures potentially leading to unconventional superconductivity. Moreover, we envisage that our approach could also be generalized to other metal carbide and nitride systems that could exhibit high-temperature superconductivity.

Construction of Ni2P-MoC/Coal-Based Carbon Fiber Self-Supporting Catalysts for Enhanced Hydrogen Evolution.

Efficient and inexpensive electrocatalysts play an important role in the hydrogen evolution reaction (HER) of electrolytic water splitting. Herein, Ni2P-MoC/coal-based carbon fiber (Ni2P-MoC/C-CF) self-supporting catalysts were obtained by low-temperature phosphorization and high-temperature carbonization. The Mo source and oxidized coal were uniformly dispersed in the carbon support by electrospinning technology. A precursor of Ni was introduced by the impregnation method. The synergistic effect of MoC and Ni2P may reduce the strong hydrogen adsorption capacity of pure MoC and provide a fast hydrogen release process. In addition, the C-CFs prepared by electrospinning can not only prevent the agglomeration of MoC and Ni2P particles at a high temperature but also provide a self-supporting support for the catalyst. As a result, the catalytic performance of the HER was improved greatly, and a low overpotential of 112 mV at 10 mA cm-2 was exhibited stably by the Ni2P-MoC/C-CFs. This work not only converts coal into coal-based carbon materials but also provides a feasible pathway for the rational design of large-scale molded hydrogen electrocatalysts.

Iron Catalyzed Cascade Construction of Molybdenum Carbide Heterointerfaces for Understanding Hydrogen Evolution.

The intercrystalline interfaces have been proven vital in heterostructure catalysts. However, it is still challenging to generate specified heterointerfaces and to make clear the mechanism of a reaction on the interface. Herein, this work proposes a strategy of Fe-catalyzed cascade formation of heterointerfaces for comprehending the hydrogen evolution reaction (HER). In the pure solid-phase reaction system, Fe catalyzes the in situ conversion of MoO2 to MoC and then Mo2 C, and the consecutive formation leaves lavish intercrystalline interfaces of MoO2 -MoC (in Fe-MoO2 /MoC@NC) or MoC-Mo2 C (in Fe-MoC/ß-Mo2 C@NC), which contribute to HER activity. The improved HER activity on the interface leads to further checking of the mechanism with density functional theory calculation. The computation results reveal that the electroreduction (Volmer step) produced H* prefers to be adsorbed on Mo2 C; then two pathways are proposed for the HER on the interface of MoC-Mo2 C, including the single-molecular adsorption pathway (Rideal mechanism) and the bimolecular adsorption pathway (Langmuir-Hinshelwood mechanism). The calculation results further show that the former is favorable, and the reaction on the MoC-Mo2 C heterointerface significantly lowers the energy barriers of the rate-determining steps.

Mo2C@C nanofibers film as durable self-supported electrode for efficient electrocatalytic hydrogen evolution.

Self-supported electrocatalytic thin films consist 3D conducting network and well-embedded electrocatalysts, which endows the advantage in mass flow kinetics and durability for large-scale water splitting. Synthesis of such self-supported electrode still remains a big challenge due to the difficulty in the control over the 3D conducting network and the simultaneous growth of catalyst with well attachment on the conducting fibers. Herein, a self-supported Mo2C@carbon nanofibers (Mo2C@C NF) film has been successfully fabricated with outstanding electrocatalytic performance under optimized pyrolysis temperature and precursors mass ratio conditions. During the carbonation process, the Mo2C nanoparticles (∼16 nm) were simultaneously grown and well dispersed on the inter-connected carbon nanofibers, which formed a 3D conducting network. The as-formed 3D carbon network was strong enough to support direct electrocatalytic application without additional ink or supporting substrates. This particular electrode structure facilitated easy access to the active catalytic sites, electron transfer, and hydrogen diffusion, resulting in the high hydrogen evolution reaction activity. A low overpotential of 86 mV was needed to achieve 10 mA cm-2current density with outstanding kinetics metric (Tafel 43 mV dec-1) in 1 M KOH. Additionally, the self-supported Mo2C@C NF film, a binder-free electrode, exhibited extraordinary stability of more than 340 h.

Dehydrogenation and dehydration of formic acid over orthorhombic molybdenum carbide.

The dehydrogenation and dehydration of formic acid is investigated on the ß-Mo2C (100) catalyst surface using time independent density functional theory. The energetics of the two mechanisms are calculated, and the thermochemistry and kinetics are discussed using the transition state theory. Subsequently, microkinetic modelling of the system is conducted, considering the batch reactor model. The potential energy landscape of the reaction shows a thermodynamically favourable cleavage of H-COOH to form CO; however, the kinetics show that the dehydrogenation mechanism is faster and CO2 is continuously formed. The effect of HCOOH adsorption on the surface is also analysed, in a temperature-programmed desorption, with the conversion proceeding at under 350 K and desorption of CO2 is observed with a selectivity of about 100 %, in line with the experimental reports.

Carbon Nanotube Supported Molybdenum Carbide as Robust Electrocatalyst for Efficient Hydrogen Evolution Reaction.

Molybdenum carbide is considered to be one of the most competitive catalysts for hydrogen evolution reaction (HER) regarding its high catalytic activity and superior corrosion resistance. But the low electrical conductivity and poor interfacial contact with the current collector greatly inhibit its practical application capability. Herein, carbon nanotube (CNT) supported molybdenum carbide was assembled via electrostatic adsorption combined with complex bonding. The N-doped molybdenum carbide nanocrystals were uniformly anchored on the surfaces of amino CNTs, which depressed the agglomeration of nanoparticles while strengthening the migration of electrons. The optimized catalyst (250-800-2h) showed exceptional electrocatalytic performance towards HER under both acidic and alkaline conditions. Especially in 0.5 M H2SO4 solution, the 250-800-2h catalyst exhibited a low overpotential of 136 mV at a current density of 10 mA/cm2 (η10) with the Tafel slope of 49.9 mV dec-1, and the overpotential only increased 8 mV after 20,000 cycles of stability test. The active corrosive experiment revealed that more exposure to high-activity γ-Mo2N promoted the specific mass activity of Mo, thus, maintaining the catalytic durability of the catalyst.