Mo Sites Research Articles

Facilitating Oriented Electron Transfer from Cu to Mo2C MXene for Weakened Mo─H Bond Toward Enhanced Photocatalytic H2 Generation.

Mo2C MXene (Mo2CTx) is recognized as an excellent cocatalyst due to unique physicochemical properties and platinum-like d-band of Mo active sites. However, Mo sites of Mo2CTx with high-density empty d-orbitals exhibit strong Mo─Hads bonds during photocatalytic hydrogen evolution, leading to easy adsorption of hydrogen ions from solution and unfavorable desorption of H2 from Mo sites. To weaken the Mo─Hads bond, a strategy of oriented electron transfer from Cu to Mo2CTx to increase the antibonding orbital occupancy of Mo─Hads hybrid orbitals is implemented by introducing Cu into Mo2CTx interlayers to form Cu-Mo2CTx. The Cu-Mo2CTx is synthesized from Mo2Ga2C and CuCl2 via a one-step molten salt method and combined with TiO2 to form Cu-Mo2CTx/TiO2 photocatalyst through an ultrasound-assisted approach. Hydrogen production tests reveal that an exceptional performance of Cu-Mo2CTx/TiO2 (6446µmol h-1 g-1, AQE=18.3%) is 8.4 fold higher than that of Mo2CF2/TiO2 (Mo2CF2 by the conventional etchant NH4F+HCl). Density functional theory (DFT) calculations and characterization results corroborate that the oriented electron transfer from Cu to Mo2CTx increases the Mo─Hads antibonding occupancy in Cu-Mo2CTx, thereby weakening Mo─Hads bonds and accelerating the hydrogen evolution rate of TiO2. This research offers valuable insights into optimizing H-adsorption capabilities at active sites on MXene materials.

MoZn-based high entropy alloy catalysts enabled dual activation and stabilization in alkaline oxygen evolution.

It remains a grand challenge to develop electrocatalysts with simultaneously high activity, long durability, and low cost for the oxygen evolution reaction (OER), originating from two competing reaction pathways and often trade-off performances. The adsorbed evolution mechanism (AEM) suffers from sluggish kinetics due to a linear scaling relationship, while the lattice oxygen mechanism (LOM) causes unstable structures due to lattice oxygen escape. We propose a MoZnFeCoNi high-entropy alloy (HEA) incorporating AEM-promoter Mo and LOM-active Zn to achieve dual activation and stabilization for efficient and durable OER. Density functional theory and chemical probe experiments confirmed dual-mechanism activation, with representative Co-Co†-Mo sites facilitating AEM and Zn-O†-Ni sites enhancing LOM, resulting in an ultralow OER overpotential (η10 = 221 mV). The multielement interaction, high-entropy structure, and carbon network notably enhance structural stability for durable catalysis (>1500 hours at 100 mA cm-2). Our work offers a viable approach to concurrently enhance OER activity and stability by designing HEA catalysts to enable dual-mechanism synergy.

Uniform anchoring of MoS2 nanosheets on MOFs-derived CoFe2O4 porous nanolayers to construct heterogeneous structural configurations for efficient and stable overall water splitting

Rational interfacial engineering and morphology modulation are recognized as effective strategies to modulate the electronic structure and improving the activity of spinel materials. In this paper, we report a strategy of Fe-induced creation of porous nanolayers of CoFe2O4 with unique morphology derived from MOFs by introducing ferrocene, and then constructed CoFe2O4/MoS2 heterostructures were fabricated by homogeneously anchoring MoS2 nanosheets onto the surface of CoFe2O4. The triple synergistic effect of heterogeneous interfaces, highly active Mo(IV) sites, and unsaturated S effectively accelerates the cycling process between Fe(III)/Fe(II) and Co(III)/Co(II), which in turn enhances the adsorption of reactive intermediates on the active sites, as further corroborates by density functional theory (DFT) calculations. As a result, the CoFe2O4/MoS2 heterostructured catalysts prepared without noble metals exhibit high catalytic performance, necessitating only 270 mV and 229 mV to achieve the current density of 100 mA·cm−2 for OER and HER respectively, which is superior to most of the reported catalysts of interest. In addition, when used in an alkaline electrolyzer, it provides a current density of 10 mA·cm−2 at 1.54 V cell voltage. This work provides a new way for the rational construction of bifunctional water electrolytic catalysts.

One-pot synthesis of amorphous high entropy Mo–C–N–O–S solids with ultradispersed Mo sites

One-pot synthesis of amorphous high entropy Mo–C–N–O–S solids with ultradispersed Mo sites

Biomimetic Elastic Single-Atom Protrusions Enhance Ammonia Electrosynthesis.

Electrocatalytic nitrogen (N2) reduction reaction (eNRR) is a promising route for sustainable ammonia (NH3) generation, but the eNRR efficiency is dramatically impeded by the sluggish reaction kinetics. Herein, inspired by the dynamic extension-contraction of sea anemone tentacles in response to environmental changes, we propose a biomimetic elastic Mo single-atom protrusion on vanadium oxide support (pSA Mo/VOH) electrocatalyst featuring a symmetry-breaking Mo site and an elastic Mo-O4 pyramid for efficient eNRR. In-situ spectroscopy and theoretical calculations reveal that the protruding Mo-induced symmetry-breaking structure optimizes the d electron filling of Mo, enhancing the back-donation to the π* antibonding orbital, effectively polarizing the N≡N bond and reducing the barrier from *N2 to *N2H. Notably, the elastic Mo-O4 pyramidal structure of pSA Mo provides a dynamic Mo-O microenvironment during continuous eNRR processes. This optimizes the electronic structure of the Mo sites based on different reaction intermediates, enhancing the adsorption of various N intermediates and maintaining low barriers throughout the six-step hydrogenation process. Consequently, the elastic pSA Mo/VOH exhibits an excellent NH3 yield rate of 50.71 ± 1.12 μg h-1 mg-1 and a Faradaic efficiency of 35.38 ± 1.03%, outperforming most electrocatalysts.

Biomimetic Elastic Single‐Atom Protrusions Enhance Ammonia Electrosynthesis

Electrocatalytic nitrogen (N2) reduction reaction (eNRR) is a promising route for sustainable ammonia (NH3) generation, but the eNRR efficiency is dramatically impeded by the sluggish reaction kinetics. Herein, inspired by the dynamic extension‐contraction of sea anemone tentacles in response to environmental changes, we propose a biomimetic elastic Mo single‐atom protrusion on vanadium oxide support (pSA Mo/VOH) electrocatalyst featuring a symmetry‐breaking Mo site and an elastic Mo−O4 pyramid for efficient eNRR. In‐situ spectroscopy and theoretical calculations reveal that the protruding Mo‐induced symmetry‐breaking structure optimizes the d electron filling of Mo, enhancing the back‐donation to the π* antibonding orbital, effectively polarizing the N≡N bond and reducing the barrier from *N2 to *N2H. Notably, the elastic Mo−O4 pyramidal structure of pSA Mo provides a dynamic Mo−O microenvironment during continuous eNRR processes. This optimizes the electronic structure of the Mo sites based on different reaction intermediates, enhancing the adsorption of various N intermediates and maintaining low barriers throughout the six‐step hydrogenation process. Consequently, the elastic pSA Mo/VOH exhibits an excellent NH3 yield rate of 50.71 ± 1.12 μg h−1 mg−1 and a Faradaic efficiency of 35.38 ± 1.03%, outperforming most electrocatalysts.

Molybdenum Carbide Catalyst Enables Efficient Conversion of Chlorinated Volatile Organic Waste into Syngas through Catalytic Steam Reforming.

Catalytic steam reforming offers a groundbreaking approach for converting industrial chlorinated volatile organic compound (CVOC) waste into valuable syngas (H2 and CO) and recovering HCl. However, the lack of C-Cl bond activation ability in traditional transition metal catalysts results in their insufficient reforming activity toward CVOCs. Herein, a novel molybdenum carbide (β-Mo2C) catalyst is developed and loaded onto a γ-Al2O3 support synthesized through a self-assembly method. The γ-Al2O3 support provides abundant unsaturated coordinated Al3+ ions, which effectively anchor and disperse β-Mo2C nanoparticles. In the catalytic steam reforming reaction at 600 °C, the β-Mo2C/γ-Al2O3 catalyst achieves a conversion efficiency higher than 95% and syngas yields of 82.4-92.3% for various typical industrial CVOCs. The mechanistic research reveals that the coordination between C and Mo atoms in β-Mo2C leads to a slightly electron-deficient state of the Mo sites, accompanied by a high density of unoccupied 4d orbitals. These characteristics are highly advantageous for the adsorption and dechlorination of CVOC molecules. The produced nonchlorinated intermediates can subsequently be oxidized to CO and H2 by hydroxyl radicals on adjacent Mo sites.

Boosting Electrocatalytic Performance of Sulfide Oxidation on Polyoxomolybdates with Synergistic Effects of CNT‐Doped Aerogel Foams

AbstractThe meticulous design of highly efficient indirect electrocatalysts with value‐added conversion properties remains a substantial challenge within the realm of organic catalysis. While polyoxometalates (POMs) serve as crucial active centers in catalytic modeling systems for chemical materials, their exploration in electrocatalytic organic molecular transformations is hindered by kinetic barriers. Therefore, an efficient protocol is established for the synthesis of electrocatalysts utilizing polyoxomolybdates (CuMo6) immobilized on aerogel foams (CMC). The electrical conductivity and electrocatalytic activities of the electrocatalyst (CuMo6/CNT@CMC) can be readily enhanced by adjusting the microenvironment between the CuMo6 and CMC using carbon nanotubes (CNT). Controlled experiments demonstrate that the CuMo6/CNT@CMC electrocatalyst for the oxidation of sulfide achieves an impressive Faradaic Efficiency (FE) exceeding 95% under ambient conditions, while the working potential is markedly lower than that of reported heterogeneous electrocatalysts. Combined experimental and theoretical analyses suggest that the modulated electronic synergistic interaction between the Cu‐assisted Mo sites and CNT within foam favors the appropriate binding of PhCH3S+• intermediates, thereby promoting the selective oxidation of sulfides. This study paves the way for the utilization of polyoxometalate‐based materials with simple synthesis methods for various electrocatalytic applications.

Synergistic Alkaline Hydrogen Evolution Catalysis over MoC Triggered by Doping Single Ru Atoms

AbstractThe rational design of single atom‐based catalysts and precise elucidation of the synergistic interaction between the metal site and substrate are pivotal to identifying the real active sites and explicating the catalytic mechanisms at the atomic scale, thus contributing to the development of high‐performance catalysts for diverse industrial implementations. Herein, a Ru single‐atom doping strategy is developed to activate the MoC substrate with superior hydrogen evolution reaction (HER) activity in an alkaline medium. The atomically dispersed Ru sites are elaborately doped into MoC nanoparticles loaded on 3D N‐doped carbon nanoflowers (Ru‐SAs@MoC/NCFs hereafter). The experimental results and theoretical calculations manifest that the atomically isolated Ru dopants can effectively trigger the Mo sites with thermodynamically favorable water adsorption/dissociation energies and facilitate the OH− desorption on Ru sites and H adsorption on N sites, thus synergistically expediating the overall alkaline HER kinetics. As such, the well‐designed Ru‐SAs@MoC/NCFs demonstrate extraordinary HER activity with a low overpotential of 16 mV at 10 mA cm−2 in 1.0 m KOH electrolyte, outperforming Pt/C benchmark and a vast of molybdenum/ruthenium‐based HER catalysts reported to date. These findings disclose the alkaline HER mechanistic induced by the atomic doping modulation and suggest a design principle of high‐efficiency electrocatalysts via the atomic‐level manipulation leverage.

Cauliflower-like Pd/MoC||Mo2C/C heterostructure as an efficient trifunctional catalyst for formic acid oxidation, hydrogen evolution, and oxygen reduction reactions

The use of Pd-based catalytic materials as electrocatalysts for formic acid oxidation reaction (FAO), hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) has been well-established for some time. The incorporation of a second phase can markedly enhance the electronic properties of the composites. The combination of different compounds with superior electronic properties is crucial for the design and preparation of catalysts with optimal catalytic activity and stability. In this study, a novel cauliflower-like Pd/MoC||Mo2C/C composite with heterostructure is synthesised, which exhibits excellent catalytic activity and long-term stability against FAO, HER, and ORR. The high-temperature treatment results in the formation of small-sized Mo₂C and MoC nanoparticles on the carbonaceous substrate, thereby exposing a greater number of Mo and Mo-C active sites. The formation of heterostructures between Mo₂C and MoC optimises the electronic structure of the composite, thereby facilitating enhanced reaction processes. In terms of FAO, the mass activity of Pd/MoC||Mo2C/C is 1.87 A mgPd−1, which is 2.75 times higher than that of Pd/C (0.68 A mgPd−1). As for the HER, a much lower overpotential of 28 mV is required to achieve a current density of 10 mA cm−2 compared to Pd/C (40 mV). Fortunately, Pd/MoC||Mo2C/C also shows excellent ORR activity with a half-wave potential of 0.798 V and the maximum current density of approximately 5.73 mA cm−2 in alkaline electrolyte. These findings may contribute to the development of other noble metal-based materials loaded on intermetallic compounds with stable and effective electrocatalytic performance.

Second-Coordination-Sphere Effects Reveal Electronic Structure Differences between the Mitochondrial Amidoxime Reducing Component and Sulfite Oxidase.

A combination of X-ray absorption and low-temperature electronic absorption spectroscopies has been used to probe the geometric and electronic structures of the human mitochondrial amidoxime reducing component enzyme (hmARC1) in the oxidized Mo(VI) and reduced Mo(IV) forms. Extended X-ray absorption fine structure analysis revealed that oxidized enzyme possesses a 5-coordinate [MoO2(SCys)(PDT)]- (PDT = pyranopterin dithiolene) active site with a cysteine coordinated to Mo. A 5-coordinate geometry is retained in the reduced state, with the equatorial oxo being protonated. Low-temperature electronic absorption spectroscopy of hmARC1 reveals a spectrum for the oxidized enzyme that is significantly different from what has been reported for sulfite oxidase family enzymes. Time-dependent density functional theory computations on oxidized and reduced hmARC1, and a small molecule analogue for hmARC1ox, have been used to assist us in making detailed band assignments and developing a greater understanding of enzyme electronic structure contributions to reactivity. Our understanding of the hmARCred HOMO and the LUMO of the benzamidoxime substrate reveal a potential π-bonding interaction between these redox orbitals, with two-electron occupation of the substrate LUMO along the reaction coordinate activating the O-N bond for cleavage and promoting oxygen atom transfer to the Mo site.

Structure engineering and surface reconstruction enabling MoNi4 hollow nanocube for efficient urea-assisted water electrolysis

Nickel-based electrocatalysts are identified as the promising candidates for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) in urea-assisted water electrolysis to accelerate energy saving hydrogen production. However, the high occupation of Ni 3d orbital leads to their constrained adsorption for reactant and multiple intermediates during UOR process. Herein, considering the d-band electron complementation, the bimetallic MoNi4 hollow nanocubes self-assembled with numerous ultrathin nanosheets was constructed by introducing molybdenum with relatively empty d orbital and synergistically boost UOR/HER activities. Notably, the MoNi4 requires a lower cell voltage of 1.462 V to drive a current density of 10 mA cm−2 in urea electrolyzer, superior to that in water electrolyzer (1.796 V) and most of the reported nickel-based electrocatalysts, as well as the urea degradation rate is impressive. In situ technologies including electrochemical impedance spectroscopies and Raman spectra reveal that the favorable UOR pathway can be initiated directly by the reconstructed NiOOH species. Density functional theory (DFT) calculations prove that the urea molecular are preferential absorbed on Ni site and then collaborate with the adjacent Mo site to carry out the subsequently dehydrogenation, N-N coupling, and desorption in energetically favorable pathways, proving their dual site mechanism (synergy between Mo and Ni).

Electronic regulation by constructing RGO/MoCQD/CF double interface to enhance performance in solar cells

The intrinsic defects such as the low electrical conductivity and sluggish kinetics for counter electrode seriously hinder its ability to meet the requirements of daily applications for dye-sensitized solar cells (DSSCs). Herein, to propel the development of DSSCs toward ultra-high stability and fast dynamics, the counter electrode (CE) of RGO/MoCQD/CF nanoreactors are created by sandwiching stable MoC quantum dots (QDs) in two distinct carbon matrices {Reduced Graphene Oxide (RGO) and Carbon Flower (CF)}. The multi-structured nanoreactors both effectively enhance stability of catalysis by forming sandwich structure and offers homogeneous dispersion of MoCQD to avoid its agglomeration. Numerous electrons assemble at the RGO contact, which can disrupt the balanced charge state and and modify the electronic structures of Mo sites to expedite reaction kinetics and I3- catalytic activity, according to studies using density functional theory and X-ray photoelectron spectroscopy. Additionally, the framework also contains the advantage of the vast uniformly dispersed active sites, a fast ion–electron transportation channel, and reactive structures that facilitate electrolyte infiltration. By virtue of integration of multiple advantages, DSSC with RGO/MoCQD/CF CE brings excellent performance, i.e., high PCE (9.08 %) and ultra-long cycling performance (96 h), offering great potential for make use of basically viable DSSC.

New Morphology Modifier Enables the Preparation of Ultra-Long Platinum Nanowires Excluding Mo Component for Efficient Oxygen Reduction Reaction Performance.

The structural tailoring of Pt-based catalysts into 1D nanowires for oxygen reduction reactions (ORR) has been a focus of research. Mo(CO)6 is commonly used as a morphological modifier to form nanowires, but it is found that it inevitably leads to Mo doping. This doping introduces unique electrochemical signals not seen in other Pt-based catalysts, which can directly reflect the stability of the catalyst. Through experiments, it is demonstrated that Mo doping is detrimental to ORR performance, and theoretical calculations have shown that Mo sites that are inherently inactive also poison the ORR activity of the surrounding Pt. Therefore, a novel gas-assisted technique is proposed to replace Mo(CO)6 with CO, which forms ultrafine nanowires with an order of magnitude increase in length, ruling out the effect of Mo. The catalyst performs at 1.24 A mgPt -1, 7.45 times greater than Pt/C, demonstrating significant ORR mass activity, and a substantial improvement in stability. The proton exchange membrane fuel cell using this catalyst provides a higher power density (0.7W cm-2). This study presents a new method for the preparation of ultra-long nanowires, which opens up new avenues for future practical applications of low-Pt catalysts in PEMFC.

Releasing Au Electrons to Mo Site for Weakened Mo─H Bond of Mo2C MXene Cocatalyst Toward Improved Photocatalytic H2 Production.

Mo2C MXene (Mo2CTx) is one of the most promising noble-metal-free cocatalysts for photocatalytic H2 production because of its excellent electron transport capacity and abundant Mo sites. However, Mo2CTx typically exhibits a strong Mo─Hads bond, resulting in that the produced H2 difficultly desorbs from the Mo surface for the limited activity. To effectively weaken the Mo─Hads bond, in this paper, a regulation strategy of electron donor Au releasing electrons to the d-orbitals of Mo sites in Mo2CTx is proposed. Herein, the Mo2CTx-Au/CdS photocatalysts are prepared through a two-step process, including the initial loading of Au nanoparticles on the Mo2CTx surface and the subsequent in situ growth of CdS onto the Mo2CTx-Au surface. Photocatalytic measurements indicate that the maximal H2-production rate of Mo2CTx-Au/CdS reaches up to 2799.44µmol g-1h-1, which is 30.99 and 3.60 times higher than that of CdS and Mo2CTx/CdS, respectively. Experimental and theoretical data corroborate that metallic Au can transfer free electrons to Mo2CTx to generate electron-enriched Moδ- sites, thus causing the increased antibonding-orbital occupancy state and the weakened Mo─Hads bond for the boosted H2-production efficiency. This research provides a promising approach for designing Mo2CTx-based cocatalysts by regulating the antibonding-orbital occupancy of Mo sites for improved photocatalytic performance.

Spatial confined synthesis of submicron Fe-MoS2 with abundant surface cationic groups and sulfur vacancies for enhanced peroxymonosulfate activation

ABSTRACT The widespread use of emerging refractory organic contaminants poses a significant threat to human health, prompting the need for a cost-effective and efficient removal strategy. While the iron ions/PMS system effectively removes organic pollutants, slow Fe3+ to Fe2+ transformation hampers its efficiency, and the homogeneous distribution of iron ions complicates separation, resulting in secondary sludge pollution. Herein, we developed a novel submicron Fe-MoS2 (S-Fe-MoS2) catalyst with abundant surface cationic groups and sulfur vacancy through a cationic polyacrylamide aerogels (CPAMA) confined hydrothermal synthesis strategy. These features promote active site exposure, enhance reactant adsorption, and accelerate electron transfer between Mo and Fe sites, improving catalytic kinetics and promoting Fe3+/Fe2+ cycle for PMS activation. As a result, the S-Fe-MoS2/PMS system exhibited a high catalytic rate constant (k obs) of 0.32 min−1, in the degradation of 4-chlorophenol (4-CP), 1.5 times higher than that of the conventional Fe-MoS2/PMS system. It also achieved 82.9% total organic carbon (TOC) degradation within 60 min. Additionally, it possessed similar degradation performance for various organic pollutants, along with remarkable reusability (four cycles) and broad pH adaptability (2–8), indicating significant potential for widespread application. This study provided a new way for developing advanced heterogeneous catalysts with high efficiency for water treatment.

Facile synthesis of defect-rich interfacial Mo/MoO2 for efficient peroxymonosulfate activation and refractory pollutants degradation

Peroxymonosulfate-based advanced oxidation process (PMS-AOP) has shown great potential in sewage purification, and catalyst development capable of efficient PMS activation is a key while challenging element. Herein we reported a facile electro-explosive route to synthesize the oxygen vacancy (Vo)-enriched Mo/MoO2 without using chemical reagents. The detailed studies suggested that the synergy of Mo active site and Vo in the catalyst significantly boosted the activation kinetics of PMS. Evidently, the Mo site of different oxidation states contributed to chemical activation of PMS, while the Vo favored the activation of PMS and the generation of non-radical 1O2 species. As a result, the Mo/MoO2-10 h/PMS system delivered a complete removal of acid orange 7 (AO7) within 4 min, significantly exceeding the activity of Mo/PMS (16%), MoO2-H/PMS (25%) and most of other PMS-based systems. Moreover, the current system showed high potential for removal of different pollutants including antibiotics and organic dyes. Radical quenching experiments and electron paramagneticresonance (EPR) studies revealed that the 1O2 species was significant for AO7 decomposition. This work provided a novel strategy to a batch-scale synthesis of high-performance PMS activator for water remediation in practice.

Engineering d-p Orbital Hybridization in Mo-O Species of Medium-Entropy Metal Oxides as Highly Active and Stable Electrocatalysts toward Ampere-Level Water/Seawater Splitting.

Optimizing the electronic structure of electrocatalysts is of particular importance to enhance the intrinsic activity of active sites in water/seawater. Herein, a series of medium-entropy metal oxides of X(NiMo)O2/NF (X = Mn, Fe, Co, Cu and Zn) is designed via a rapid carbothermal shocking method. Among them, the optimized medium-entropy metal oxide (FeNiMo)O2/NF delivered remarkable HER performance, where the overpotentials as low as 110 and 141mV are realized at 1000 mAcm-2 (@60°C) in water and seawater. Meanwhile, medium-entropy metal oxide (FeNiMo)O2/NF only required overpotentials of as low as 330 and 380mV to drive 1000mAcm-2 for OER in water and seawater (@60°C). Theoretical calculations showed that the multiple-metal synergistic effect in medium-entropy metal oxides can effectively enhance the d-p orbital hybridization of Mo─O bond, reduce the energy barrier of H* adsorbed at the Mo sites. Meanwhile, Fe sites in medium-entropy metal oxide can act as the real OER active center, resulting in a good bifunctional activity. In all, this work provides a feasible strategy for the development of highly active and stable medium-entropy metal oxide electrocatalysts for ampere-level water/seawater splitting.

Biaxial strain induced OH engineer for accelerating alkaline hydrogen evolution

The sluggish kinetics of Volmer step in the alkaline hydrogen evolution results in large energy consumption. The challenge that has yet well resolved is to control the water adsorption and dissociation. Here, we develop biaxially strained MoSe2 three dimensional nanoshells that exhibit enhanced catalytic performance with a low overpotential of 58.2 mV at 10 mA cm−2 in base, and long-term stable activity in membrane-electrode-assembly based electrolyser at 1 A cm−2. Compared to the flat and uniaxial-strained MoSe2, we establish that the stably adsorbed OH engineer on biaxially strained MoSe2 changes the water adsorption configuration from O-down on Mo to O-horizontal on OH* via stronger hydrogen bonds. The favorable water dissociation on 3-coordinated Mo sites and hydrogen adsorption on 4-coordinated Mo sites constitute a tandem electrolysis, resulting in thermodynamically favorable hydrogen evolution. This work deepens our understanding to the impact of strain dimensions on water dissociation and inspires the design of nanostructured catalysts for accelerating the rate-determining step in multi-electron reactions.

Activation of inert surface of monolayer MoS2 by transition metal and nitrogen co-doping to promote hydrogen evolution reaction

In this work, we systematically investigate the possible H adsorption sites, charge density difference, partial density of states, p-band center and Bader charge of transition metal (TM) and nitrogen (N) co-doped monolayer MoS2. The results show that the equilibrium of H adsorption and desorption can be achieved in TM-N co-doped monolayer MoS2. The ΔGH at the S site of Co-N co-doped system is −0.05 eV, which is better than that of traditional Pt site (ΔGH=-0.09 eV) and Mo site at the MoS2 edge (ΔGH=0.08 eV). This work has important implications for designing more efficient electrocatalysts.