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.

Enhancing bacterial control and daylight-driven water remediation with chitosan-impregnated MoC nanosheets.

The functionalization of nanoparticles with 2D nanosheets is an effective approach to enhance their functional properties for pollutant removal. This research outlines the synthesis of a 2D-delaminated molybdenum carbide (MXene) chitosan nanocomposite (2D-d-Mo2CTx-Cs NC) with bacterial control and photocatalytic properties for dye adsorption. The nanocomposite includes Tx-surface terminating groups O, OH, and F. In this investigation, the composite was synthesized using the etching method and its formation was confirmed through UV spectra at 288 nm. It was characterized through FTIR, XRD, Particle size, Zetapotential, FESEM, HRTEM, EDAX, and XPS analyses. FTIR spectral analysis of NC suggests that amines are formed through a Schiff base reaction between glutaraldehyde and Cs, or through the interaction of terminal aldehydes and carbonyl groups. The XRD analysis confirmed the crystalline structure of the composite. FESEM images revealed irregularly structured nanosheets (NSs) material in the prepared 2D-d-Mo2CTx-Cs NC samples. HRTEM images revealed 2D-d-Mo2CTx NSs impregnated onto Cs with an average size of 50 nm, as confirmed by a particle size analyzer, with a zeta potential value of - 15 mV. Additionally, Mo, C, N, and O are the most significant elements present in the NC, as confirmed by EDAX and XPS analyses. Further, biocompatibility testing of 2D-d-Mo2CTx-Cs NC yielded positive results. Moreover, under sunlight, the composites effectively adsorbed methylene blue with a 90% adsorption capacity, as confirmed by kinetic studies. Furthermore, the synergistic effect of Cs and d-Mo2CTx NSs resulted in significant antibacterial (50-200 µl of 1 mg/ml) and antibiofilm activity (100 µl of 1 mg/ml) against pathogenic bacteria. Furthermore, this study represents the first report on the use of 2D-d-Mo2CTx-Cs NC for daylight-influenced photocatalytic applications with a bacteria-controlling effect.

All-MXene electronic tongue for neurotransmitters detection.

Neurotransmitters (NTs) are molecules produced by neurons that act as the body's chemical messengers. Their abnormal levels in the human system have been associated with many disorders and neurodegenerative diseases, which makes the monitoring of NTs fundamentally important. Specifically for clinical analysis and understanding of brain behavior, simultaneous detection of NTs at low levels quickly and reliably is imperative for disease prevention and early diagnosis. However, the methods currently employed are usually invasive or inappropriate for multiple NTs detection. Herein, we developed a MXene-based impedimetric electronic tongue (e-tongue) for sensitive NT monitoring, using Nb2C, Nb4C3, Mo2C, and Mo2Ti2C3 MXenes as sensing units of the e-tongue, and Principal Component Analysis (PCA) as the data treatment method. The high specific surface area, distinct electrical properties, and chemical stability of the MXenes gave rise to high sensitivity and good reproducibility of the sensor array toward NT detection. Specifically, the e-tongue detected and differentiated multiple NTs (acetylcholine, dopamine, glycine, glutamate, histamine, and tyrosine) at concentrations as low as 1 nmol L-1 and quantified NTs present in a mixture. Besides, analyses performed with interferents and actual samples confirmed the system's potential to be used in clinical diagnostics. The results demonstrate that the MXene-based e-tongue is a suitable, rapid, and simple method for NT monitoring with high accuracy and sensitivity.

Self-supported porous wood carbon electrode with a MoC/carbon nanocage composite for application in a high-performance supercapacitor.

The rational design and synthesis of carbon nanocages with highly complex porous structures are continuously facing challenges in the development of high-performance supercapacitors (SCs). The electrochemical performance characteristics of electrodes rely on their compositions and fabrication methods. Here, we propose a universal and efficient approach for the in-situ synthesis of zeolitic imidazolate framework-8 (ZIF-8) on porous carbonized wood, where the selective utilization of hexacarbonyl molybdenum protects the structural integrity of the ZIF-8 precursor, preventing collapse during thermal treatment. The subsequent pyrolysis process leads to the formation of small-sized molybdenum carbide (MoC) which are embedded in carbon nanocages (CN). The composite electrode consists of MoC/CN embedded in a porous carbonized wood (PCW), and it shows area-specific capacity of 9.7F cm-2 and 9.4 F cm-2 at 5 mA cm-2 and 30 mA cm-2, respectively. Subsequently, the symmetric supercapacitor, with two MoC/CN@PCW electrodes exhibits a areal specific capacitance of 2.7 F cm-2 at 5 mA cm-2. Moreover, this supercapacitor maintains an capacitance retention rate of 98.5 % after 12,000 discharge cycles. The supercapacitor exhibits a power density of 6.5 mW cm-2, resulting in an energy density of 0.864 mWh cm-2. Therefore, the utilization of wood-based electrodes holds promise for energy storage systems.

Electron-deficient Co7Fe3 induced by interfacial effect of molybdenum carbide boosting oxygen evolution reaction.

Developing a high-activity and low-cost catalyst to reduce the anodic overpotential is essential for hydrogen production from water splitting. In this work, a hetero-structured Co7Fe3/Mo2C@C catalyst has been developed to efficiently catalyze oxygen evolution reaction (OER), the overpotential (ƞ10) of Co7Fe3/Mo2C@C-catalyzed OER with current density of 10 mA/cm2 is about 254 mV, substantially lower than the counterparts of Co7Fe3@C-catalyzed OER (ƞ10, 308 mV) and Mo2C@C-catalyzed OER (ƞ10, 439 mV), close to that of OER catalyzed by commercial RuO2. The mechanistic studies reveal that the distinct electron transfer across the Co7Fe3/Mo2C interface results in electron-deficient Co7Fe3, which has been identified as the highly active catalytic sites. Density functional theory (DFT) calculations manifest that Mo2C induces a distinct decrease in electron density on Co7Fe3 and upgrades the d-band centers of Co and Fe in Co7Fe3 towards Fermi energy level, thus substantially lowering the energy barrier of the rate-determining reaction step and conferring significantly improved OER activity on the Co7Fe3/Mo2C@C catalyst.

Addressing adsorption and catalysis of lithium polysulfide via electronic distribution of molybdenum carbide host.

Heterostructure engineering is considered a crucial strategy to modulate the intrinsic charge transfer behavior of materials, enhance catalytic activity, and optimize sulfur electrochemical processes. However, parsing the role of heterogeneous interface-structure-property relationships in heterostructures is still a key scientific issue to realize the efficient catalytic conversion of polysulfides. Based on this, molybdenum carbide (Mo2C) was successfully partial reduced to molybdenum metal (Mo) via a thermal reduction at high-temperature and the typical Mo-Mo2C-based Mott-Schottky heterostructures were simultaneously constructed, which realized the modulation of the electronic structure of Mo2C and optimized the conversion process of lithium polysulfides (LPS). Compared with single molybdenum carbide, the modulated molybdenum carbide acts as an electron donor with stronger Mo-S bonding strength as well as higher polysulfide adsorption energy, faster Li2S conversion kinetics, and greatly facilitates the adsorption → catalysis process of LPS. As a result, yolk-shell Mo-Mo2C heterostructure (C@Mo-Mo2C) exhibits excellent cycling performance as a sulfur host, with a discharge specific capacity of 488.41 mAh g-1 for C@Mo-Mo2C/S at 4 C and present an excellent high-rate cyclic performance accompanied by capacity decay rate of 0.08 % per cycle after 400 cycles at 2 C. Heterostructure-acting Mo2C electron distribution modulation engineering may contributes to the understanding of the structure-interface-property interaction law in heterostructures and further enables the efficient modulation of the chemical behavior of sulfur.

Enhanced Catalytic Hydrogenation of Olefins in Sulfur-Rich Naphtha Using Molybdenum Carbide Supported on γ-Al2O3 Spheres under Steam Conditions: Simulating the Hot Separator Stream Process.

Spheres comprising 10 wt.% Mo2C/γ-Al2O3, synthesized through the sucrose route, exhibited unprecedented catalytic activity for olefin hydrogenation within an industrial naphtha feedstock that contained 23 wt.% olefins, as determined by supercritical fluid chromatography (SFC). The catalyst demonstrated resilience to sulfur, exhibiting no discernible deactivation signs over a tested 96 h operational period. The resultant hydrogenated naphtha from the catalytic process contained only 2.5 wt.% olefins when the reaction was conducted at 280 °C and 3.44 × 106 Pa H2, subsequently blended with Athabasca bitumen to meet pipeline specifications for oil transportation. Additionally, the carbide catalyst spheres effectively hydrogenated olefins under steam conditions without experiencing any notable hydrogenation in the aromatics. We propose the supported carbide catalyst as a viable alternative to noble metals, serving as a selective agent for olefin elimination from light petroleum distillates in the presence of steam and sulfur, mitigating the formation of gums and deposits during the transportation of diluted bitumen (dilbit) through pipelines.

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).

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.

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.

Nickel Nanoparticles Protruding from Molybdenum Carbide Micropillars with Carbon Layer-Protected Biphasic 0D/1D Heterostructures for Efficient Water Splitting.

It remains a tremendous challenge to achieve high-efficiency bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) for hydrogen production by water splitting. Herein, a novel hybrid of 0D nickel nanoparticles dispersed on the one-dimensional (1D) molybdenum carbide micropillars embedded in the carbon layers (Ni/Mo2C@C) was successfully prepared on nickel foam by a facile pyrolysis strategy. During the synthesis process, the nickel nanoparticles and molybdenum carbide were simultaneously generated under H2 and C2H2 mixed atmospheres and conformally encapsulated in the carbon layers. Benefiting from the distinctive 0D/1D heterostructure and the synergistic effect of the biphasic Mo2C and Ni together with the protective effect of the carbon layer, the reduced activation energy barriers and fast catalytic reaction kinetics can be achieved, resulting in a small overpotential of 96 mV for the HER and 266 mV for the OER at the current density of 10 mA cm-2 together with excellent durability in 1.0 M KOH electrolyte. In addition, using the developed Ni/Mo2C@C as both the cathode and anode, the constructed electrolyzer exhibits a small voltage of 1.55 V for the overall water splitting. The novel designed Ni/Mo2C@C may give inspiration for the development of efficient bifunctional catalysts with low-cost transition metal elements for water splitting.

Innovative flow-through reaction system for the sustainable production of phenolic monomers from lignocellulose catalyzed by supported Mo2C.

Molybdenum carbide supported on activated carbon (ß-Mo2C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow-Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT-RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT-RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13-15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT-RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two-step non-equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs.

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.

Bimetallic metal-organic framework-derived bamboo-like N-doped carbon nanotube-encapsulated Ni-doped MoC nanoparticles for water oxidation.

Molybdenum carbide materials with unique electronic structures have received special attention as water-splitting catalysts, but their structural stability in the alkaline water electrolysis process is not satisfactory. This study reports an in situ pyrolysis method for preparing NiMo-based metal-organic framework (MOF)-derived chain-mail oxygen evolution reaction (OER) electrocatalysts and bamboo-like N-doped carbon nanotube (NCNT)-encapsulated Ni-doped MoC nanoparticles (NiMoC-NCNTs). The NCNTs can provide chain mail shells to protect the inner highly reactive Ni-doped MoC cores from electrochemical corrosion by the alkaline electrolyte and regulate their catalytic properties through charge redistribution. Benefiting from high N-doping with abundant pyridinic moieties and abundant active sites of the periodic bamboo-like nodes, the as-prepared NiMoC-NCNTs display an outstanding activity for the OER with an overpotential of 310 mV at 10 mA cm-2 and a superior long-term stability of 50 h. Density functional theory calculations reveal that the excellent electrocatalytic activity of NiMoC-NCNTs comes from the electron transfer from NiMoC nanoparticles to NCNTs, resulting in a decrease in the local work function at the carbon surface and optimized free efficiencies of OER intermediates on C sites. This work provides an effective approach to improve the structural stability of fragile catalysts by equipping them with carbon-based chain.

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.

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.

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.

Influence of Carbonization Conditions on Structural and Surface Properties of K-Doped Mo2C Catalysts for the Synthesis of Methyl Mercaptan from CO/H2/H2S.

The cooperative transition of sulfur-containing pollutants of H2S/CO/H2 to the high-value chemical methyl mercaptan (CH3SH) is catalyzed by Mo-based catalysts and has good application prospects. Herein, a series of Al2O3-supported molybdenum carbide catalysts with K doping (denoted herein as K-Mo2C/Al2O3) are fabricated by the impregnation method, with the carbonization process occurring under different atmospheres and different temperatures between 400 and 600 °C. The CH4-K-Mo2C/Al2O3 catalyst carbonized by CH4/H2 at 500 °C displays unprecedented performance in the synthesis of CH3SH from CO/H2S/H2, with 66.1% selectivity and a 0.2990 g·gcat-1·h-1 formation rate of CH3SH at 325 °C. H2 temperature-programmed reduction, temperature-programmed desorption, X-ray diffraction and Raman and BET analyses reveal that the CH4-K-Mo2C/Al2O3 catalyst contains more Mo coordinatively unsaturated surface sites that are responsible for promoting the adsorption of reactants and the desorption of intermediate products, thereby improving the selectivity towards and production of CH3SH. This study systematically investigates the effects of catalyst carbonization and passivation conditions on catalyst activity, conclusively demonstrating that Mo2C-based catalyst systems can be highly selective for producing CH3SH from CO/H2S/H2.

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.

Synergistic Effect of Dual-Doped Carbon on Mo2C Nanocrystals Facilitates Alkaline Hydrogen Evolution.

Molybdenum carbide (Mo2C) 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 sites 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 Mo2C nanocrystals (Mo2C@BNC) for accelerating HER under alkaline condition. The electronic interactions between the Mo2C 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 H2O adsorption sites for the water-cleaving step. Accordingly, the dual-doped Mo2C 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.