Structural change of molybdenum sulfide facilitates the electrocatalytic hydrogen evolution reaction at neutral pH as revealed by in situ Raman spectroscopy

Molybdenum sulfides are promising electrocatalysts for the hydrogen evolution reaction(HER).Sand Mo‐related species have been proposed as the active site for forming adsorbed hydrogen to initiate the HER;however,the nature of the interaction between Mo centers and S ligands is unclear.Further,the development of cost‐effective water‐splitting systems using neutral water as a proton source for H2evolution is highly desirable,whereas the mechanism of the HER at neutral pH is rarely discussed.Here,the structural change in the Mo?Mo and S?S species in a synthesized molybdenum sulfide was monitored at neutral pH using in situ electrochemical Raman spectroscopy.Analysis of the potential dependent Raman spectra revealed that the band assigned to a terminal S?S species emerged along with synchronized changes in the frequency of the Mo?Mo,Mo3?μ3S,and Mo?S vibrational bands.This indicates that Mo?Mo bonds and terminal S?S ligands play synergistic roles in facilitating hydrogen evolution,likely via the internal reorganization of trinuclear Mo3?thio species.The nature and role of metal‐ligand interactions in the HER revealed in this study demonstrated a mechanism that is distinct from those reported previously in which the S or Mo sites function independently.

First-Principles Study of Ultrathin Molybdenum Sulfides Nanowires:Electronic and Catalytic Hydrogen Evolution Properties

Molybdenum sulfides nanomaterials, such as one-dimensional (1D) nanotubes, nanoribbons, and two-dimensional (2D) nanosheets, have attracted intensive research interests for their novel electronic, optical, and catalytic properties. On the basis of first-principles calculation, here, we report a new series of 1D ultrathin molybdenum sulfides nanowires, including Mo2S6、Mo3S6 and Mo6S10 nanowires. Our results demonstrate that these ultrathin nanowires are both thermal and lattices dynamically stable, confirmed with the calculated phonon spectrum and Born-Oppenheimer molecular dynamic simulation at the temperature up to 600 K. The calculated elastic constant is 21.33, 103.22, and 163.00 eV/■ for Mo2S6, Mo3S6, and Mo6S10 nanowires, respectively. Mo2S6 and Mo3S6 nanowires are semiconductors with band gap of 1.55 and 0.46 eV, while Mo6S10 nanowires is metal, implying their potential applications in electronics and optoelectronics. In particular, ultrathin molybdenum sulfides nanowires can be used as catalysts for hydrogen evolution reaction. The calculated Gibbs free energy change for hydrogen evolution is about -0.05 eV for Mo2S6 nanowire, comparable with those of Pt and H-MoS2. The prediction of these 1D molybdenum sulfides nanowires may enrich the 1D family molybdenum sulfides and make a supplement to understand the high performance of hydrogen evolution reaction in transition-metal dichalcogenides.

Amorphous molybdenum sulfide and its Mo-S motifs:Structural characteristics,synthetic strategies,and comprehensive applications

Amorphous materials are one kind of nonequilibrium materials and have become one of the most active research fields.Compared with crystalline solids,the theory of amorphous materials is still in infancy because their characteristic of atomic arrangement is more like liquid and has no long-range periodicity.Recently,as the representative of amorphous materials,amorphous molybdenum sulfide(a-MoS_(x))with unique physical and chemical properties has been studied extensively.However,considerable debate surrounds the structure–property relationships of a-MoS_(x)owing to its diverse Mo-S motifs.Herein,we summarize recent discoveries and research results regarding a-MoS_(x),whose structural characteristics,synthetic strategies,formation criteria,and comprehensive applications are discussed in detail.Finally,this review is ended with our personal insights and critical outlooks over the development of a-MoS_(x).

Nitrogen incorporated nickel molybdenum sulfide as efficient electrocatalyst for overall water splitting

Developing bifunctional electrocatalysts with improved efficiency and stability in overall water splitting is of extreme importance for renewable energy utilization.In this work,an in situ N doping strategy was demonstrate to boost the efficiency and stability of nickel molybdenum sulfide both in electrocatalytic hydrogen evolution reaction and oxygen evolution reaction.Experimental and theoretical results indicate that such modification offers enriched active sites for electrochemical reaction,and further increases the kinetic driven force of water electrolysis.As a result,the N–NiMoS electrode exhibits a remarkably improved performance with rather low potential of 1.54 V to offer a current density of 10 mA cm;for overall water splitting,which is 130 mV decrease than that of pristine one.In addition,impressive electrochemical stability also reveals a 76.6%preservation of initial current density after 100 h test,which is superior than that of pristine one after 25 h test.Therefore,the potential to enhance the performance of electrocatalysts by as-proposed route promises a valuable way to develop efficient catalysts with enhanced property for electrochemical applications.

Interface electronic engineering of molybdenum sulfide/MXene hybrids for highly efficient biomimetic sensors

Interface regulation plays a key role in the electrochemical performance for biosensors.By controlling the interfacial interaction,the electronic structure of active species can be adjusted effectively at micro and nano-level,which results in the optimal reaction energy barrier.Herein,we propose an interface electronic engineering scheme to design a strongly coupled 1T phase molybdenum sulfide(1T-MoS2)/MXene hybrids for constructing an efficient electrocatalytic biomimetic sensor.The local electronic and atomic structures of the 1T-MoS2/Ti3C2TX are comprehensively studied by synchrotron radiation-based X-ray photoelectron spectroscopy(XPS),as well as X-ray absorption spectroscopy(XAS)at atomic level.Experiments and theoretical calculations show that there are interfacial stresses,atomic defects and adjustable bond-length between MoS2/MXene nanosheets,which can significantly promote biomolecular adsorption and rapid electron transfer to achieve excellent electrochemical activity and reaction kinetics.The 1T-MoS2/Ti3C2TX modified electrode shows ultra high sensitivity of 1.198μA/μM for dopamine detection with low limit of 0.05μM.We anticipate that the interface electronic engineering investigation could provide a basic idea for guiding the exploration of advanced biosensors with high sensitivity and low detection limit.

Surfactant-assisted hydrothermally synthesized MoS_2 samples with controllable morphologies and structures for anthracene hydrogenation

MoS_2 samples with controllable morphologies and structures were synthesized using surfactantassisted hydrothermal processes.The effects of surfactants（PEG,PVP,P123,SDS,AOT,and CTAB）on the morphologies and structures of MoS_2 samples were investigated.The results revealed that spherical,bulk-like,and flower-like MoS_2 particles assembled by NH4~＋-intercalated MoS_2 nano-sheets were synthesized.The morphologies of the MoS_2 samples and their structures（including the slab length and the number of stacked layers） of MoS_2 nano-sheets in these samples could be controlled by adjusting the surfactants.Mono-dispersed spherical MoS_2 particles could be synthesized with PEG via the creation of MoS_2 nano-sheets with slab lengths shorter than 15 nm and fewer than six stacked layers.Possible formation mechanisms of these MoS_2 samples created via surfactant-assisted hydrothermal processes are proposed.Further,the catalytic activities of MoS_2 samples for anthracene hydrogenation were evaluated in a slurry-bed reactor.The catalyst synthesized with the surfactant PEG exhibited the highest catalytic hydrogenation activity.Compared with the other catalysts,it had a smaller particle size,mono-dispersed spherical morphology,shorter slab length,and fewer stacked layers;these were all beneficial to exposing its active edges.This work provides an efficient approach to synthesize transition metal sulfides with controllable morphologies and structures.

Depressing behaviors and mechanism of disodium bis(carboxymethyl) trithiocarbonate on separation of chalcopyrite and molybdenite

This work focuses on the organic depressant,disodium bis(carboxymethyl)trithiocarbonate(DBT),as a selectivedepressant in copper?molybdenum sulfide flotation separation.Micro-flotation,Zeta potential,FTIR and XPS measurements werecarried out to investigate the selective depression mechanism of DBT on chalcopyrite.Zeta potential and FTIR measurementsrevealed that DBT had higher affinity for chalcopyrite than molybdenite and the XPS results of chalcopyrite before and aftertreatment with DBT further proved that DBT adsorbed on chalcopyrite surface.The investigation indicates that the mechanism ofDBT adsorbing on chalcopyrite is mainly physical adsorption.Locked circuit experiments were carried out and the results showedthat DBT could be considered as a cleaner option in commercial Cu?Mo flotation separation circuits.

Low-cost solid FeS lubricant as a possible alternative to MoS2 for producing Fe-based friction materials

Three reaction systems of MoS_2-Fe, FeS -Fe, and Fe S-Fe-Mo were designed to investigate the use of FeS as an alternative to MoS_2 for producing Fe-based friction materials. Samples were prepared by powder metallurgy, and their phase compositions, microstructures, mechanical properties, and friction performance were characterized. The results showed that MoS_2 reacts with the matrix to produce iron-sulfides and Mo when sintered at 1050°C. Iron-sulfides produced in the MoS_2-Fe system were distributed uniformly and continuously in the matrix, leading to optimal mechanical properties and the lowest coefficient of friction among the systems studied. The lubricity observed was hypothesized to originate from the iron-sulfides produced. The Fe S-Fe-Mo system showed a phase composition, porosity, and density similar to those of the MoS_2-Fe system, but an uneven distribution of iron-sulfides and Mo in this system resulted in less-optimal mechanical properties. Finally, the Fe S-Fe system showed the poorest mechanical properties among the systems studied because of the lack of Mo reinforcement. In friction tests, the formation of a sulfide layer contributed to a decrease in coefficient of friction（COF） in all of the samples.

Confined synthesis of MoS_(2) with rich co-doped edges for enhanced hydrogen evolution performance

Activating MoS_(2) with atomic metal doping is promising to harvest desirable Pt-matched hydrogen evolution reaction(HER)catalytic performance.Herein,we developed an efficient method to access edgerich lattice-distorted MoS_(2) for highly efficient HER via in-situ sulphuration of atomic Co/Mo species that were well-dispersed in a formamide-derived N-doped carbonaceous(f-NC)substrate.Apart from others,pre-embedding Co/Mo species in f-NC controls the release of metal sources upon annealing in S vapor,grafting the as-made MoS_(2) with merits of short-range crystallinity,distorted lattices,rich defects,and more edges exposed.The content of atomic Co species embedded in MoS_(2) reaches up to 2.85 at.%,and its atomic dispersion has been systematically confirmed by using XRD,HRTEM,XPS,and XAS characterizations.The Co-doped MoS_(2) sample exhibits excellent HER activity,achieving overpotentials of 67 and155 m V at j=10 m A cm^(-2) in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.Density functional theory simulations suggest that,compared with free-doping MoS_(2),the edged Co doping is responsible for the significantly improved HER activity.Our method,in addition to providing reliable Pt-matched HER catalysts,may also inspire the general synthesis of edge-rich metal-doped metal chalcogenide for a wide range of energy conversion applications.

MoS_3 loaded TiO_2 nanoplates for photocatalytic water and carbon dioxide reduction

Photocatalytic water splitting and carbon dioxide reduction provide us clean and sustainable energy resources. The carbon dioxide reduction is also the redemption of the greenhouse effect. MoS/TiOphotocatalysts based on TiOnanoplates have been synthesized via a hydrothermal acidification route for water and carbon dioxide reduction reactions. This facile approach generates well dispersed Mo S3 with low crystallinity on the surface of TiOnanoplates. The as-synthesized MoS/TiOphotocatalyst showed considerable activity for both water reduction and carbon dioxide reduction. The thermal treatment effects of TiO, the loading percentage of MoSand the crystalline phase of TiOhave been investigated towards the photocatalytic performance. TiOnanoplate synthesized through hydrothermal reaction with the presence of HF acid is an ideal semiconductor material for the loading of MoSfor photocatalytic water and carbon dioxide reduction simultaneously in EDTA sacrificial solution.

DFT Study on the Electronic and Structural Properties of MoS_6^(-/0) Clusters

Density functional theory （DFT） calculations are employed to investigate the structural and electronic properties of MoS6^- and MoS6 clusters. Generalized Koopmans＇ theorem is applied to predict the vertical detachment energies and simulate the photoelectron spectra （PES）. Intriguingly, the terminal S2-, polysulfide S2^2- and S3^2- ligands simultaneously emerge in the lowest-energy structure of MoS6. Molecular orbital analyses are performed to analyze the chemical bonding in MoS6^-/0 clusters and elucidate their structural and electronic properties.

Synergistically coupling of Ni–Fe LDH arrays with hollow Co–Mo sulfide nanotriangles for highly efficient overall water splitting

Developing bifunctional catalysts that can catalyze both oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is pivotal to commercializing large-scale water splitting.Herein,a novel hollow nanotriangle composed of NiFe LDH-CoMoS_(x) heterojunction(H-CMSx@NiFe LDH)is proposed as a highly efficient bifunctional electrocatalyst for both OER and HER.To fabricate a heterojunction system,ultra-thin nickel–iron layered double hydroxide(NiFe LDH)nanosheets are uniformly electrodeposited onto a metal–organic framework-derived hollow CoMoS_(x) nanotriangle.The strong coupling of CoMoS_(x) and NiFe LDH catalysts forms the intimate heterojunction interfaces to facilitate interfacial charge transfer,which is favorable to enhance the bifunctional catalytic activity.Moreover,the large void of CoMoS_(x) nanotriangles and interconnected ultra-thin NiFe LDH nanosheets result in good electrolyte penetration and gas release.Therefore,the as-prepared H-CMSx@NiFe LDH on nickel foam(NF)exhibits an impressive catalytic activity and durability for OER and HER activities,delivering a current density of 100 mA·cm^(−2) at the small overpotentials of 214 and 299 mV in OER and HER,respectively.Meanwhile,H-CMSx@NiFe LDH/NF proves to be an effective electrode for an alkaline electrolyzer,as a voltage of only 1.99 V is enough to achieve a current density voltage of only 1.99 V is enough to achieve a current density of 400 mA·cm^(−2) with no degradation in performance over 50 h.

Efficient solar fuel production enabled by an iodide oxidation reaction on atomic layer deposited MoS_(2)

Oxygen evolution reaction(OER)as a half-anodic reaction of water splitting hinders the overall reaction efficiency owing to its thermodynamic and kinetic limitations.Iodide oxidation reaction(IOR)with low thermodynamic barrier and rapid reaction kinetics is a promising alternative to the OER.Herein,we present a molybdenum disulfide(MoS_(2))electrocatalyst for a high-efficiency and remarkably durable anode enabling IOR.MoS_(2)nanosheets deposited on a porous carbon paper via atomic layer deposition show an IOR current density of 10 mA cm^(–2)at an anodic potential of 0.63 V with respect to the reversible hydrogen electrode owing to the porous substrate as well as the intrinsic iodide oxidation capability of MoS_(2)as confirmed by theoretical calculations.The lower positive potential applied to the MoS_(2)-based heterostructure during IOR electrocatalysis prevents deterioration of the active sites on MoS_(2),resulting in exceptional durability of 200 h.Subsequently,we fabricate a two-electrode system comprising a MoS_(2)anode for IOR combined with a commercial Pt@C catalyst cathode for hydrogen evolution reaction.Moreover,the photovoltaic–electrochemical hydrogen production device comprising this electrolyzer and a single perovskite photovoltaic cell shows a record-high current density of 21 mA cm^(–2)at 1 sun under unbiased conditions.

Probing Diverse Disulfur Ligands in the Mo_2S_n^(–/0)(n = 4 ～ 8) Clusters: Structural Evolution and Chemical Bonding

Density functional theory （DFT） and coupled cluster theory （CCSD（T）） calcula-tions were employed to investigate the geometric and electronic structures of a range of dinuclearmolybdenum sulfide clusters, Mo2S,- and Mo2S,^-/0（n = 4-8）. The results showed that the sulfuratoms tended to occupy the terminal sites of the clusters continuously in the process of sequentialsulfidation. After the oxidation state of Mo atoms reached the maximum of ＋6, diverse disulfurligands emerged in the sulfur-rich Mo2S^-/0 （n = 7,8） clusters. The driving forces of removing asulfur atom from different S ligands in Mo2S^-/0 （n = 4-8） clusters, especially from those disulfurunits, were evaluated. The corresponding order may provide insight into the pretreatment of freshMoS2 catalysts. Vertical detachment energies （VDEs） were predicted according to the GeneralizedKoopmans＇ theorem, and then the photoelectron spectra （PES） were simulated. Molecular orbitaland spin density values were analyzed to elucidate the chemical bonding and the evolutionarybehavior in the dinuclear molvbdenum sulfide clusters.

Interfacial engineering of heterostructured carbon-supported molybdenum cobalt sulfides for efficient overall water splitting

Constructing hetero-structured catalyst is promising but still challenging to achieve overall water splitting for hydrogen production with high efficiency.Herein,we developed a sulfide-based MoS_(2)/Co_(l-x)S@C hetero-structure for highly efficient electrochemical hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The carbon derived from the filter paper acts as a conducting carrier to ensure adequate exposure of the active sites guaranteed with improved catalytic stability.The unique hierarchical nano-sheets facilitate the charge and ion transfer by shortening the diffusion path during electro-catalysis.Meanwhile,the robust hetero-interfaces in MoS_(2)/Co_(1-x)S@C can expose rich electrochemical active sites and facilitate the charge transfer,which further cooperates synergistically toward electro-catalytic reactions.Consequently,the optimal MoS_(2)/Co_(1-x)S@C hetero-structures present small over-potentials toward HER(135 mV@10 mA·cm^(-2))and OER(230 mV@10 mA·cm^(-2)).The MoS_(2)/Co_(1-x)S@C electrolyzer requires an ultralow voltage of 1.6 V at the current density of 10 mA·cm^(-2)with excellent durability,outperforming the state-of-the-art electro-catalysts.This work sheds light on the design of the hetero-structured catalysts with interfacial engineering toward large-scale water splitting.

MoS2 yolk-shell microspheres with a hierarchical porous structure for efficient hydrogen evolution

Yolk-shell architectures have attracted extensive attention owing to their unique structure and infusive applications. MoS2 is regarded as one of the most promising catalytic materials for hydrogen evolution by the splitting of water. In this work, a simple self-template solvothermal approach is developed for the synthesis of novel MoS2 yolk-shell microspheres with a hierarchical porous structure by reacting MoO2 microspheres with L-cysteine. A dissolution- recrystallization formation mechanism is proposed for the MoS2 yolk-shell microspheres. Owing to structural superiority, the new material architecture exhibits improved photoelectrochemical properties, including efficient hydrogen evolution reaction catalytic activities, a high photocurrent density, a small overpotential, and a low charge-transfer resistance.

Composite separator based on PI film for advanced lithium metal batteries

Lithium(Li) metal batteries have received extensive research focusing on the dendrite growth issue on account of the high chemical activity of Li anode. While, thermal safety, as one of the important security concerns facing the further application, gets little attention. Here, the high-performance polyimide film is successfully developed to enhance the safety margin based on the excellent mechanical strength and heat resistance corresponding to the traditional separator. And, the polyimide film with the Mo S2 coating made by spraying method as the composite separator can not only improve the wettability to the electrolyte, but also in-situ form an artificial layer with the low nucleation barrier for the Li ions. When used in both the coin cell and the pouch cell, all achieve the outstanding cycling stability and the coulombic efficiency. Specially, the in-situ Li ions nucleation behaviors are investigated by optical microscopy in the capillary cell. The electric field intensity at the Li anode surface is also simulated by COMSOL Multiphysics to further elucidate the effect of the coating.

"Small amount for multiple times" of H_(2)O_(2) feeding way in MoS_(2)-Fex heterogeneous fenton for enhancing sulfadiazine degradation

In recent years, MoS_(2) catalyzed/cocatalyzed Fenton/Fenton-like systems have attracted wide attention in the field of pollution control, but there are few studies on the effect of H_(2)O_(2) feeding way on the whole Fenton process. Here, we report a new type of composite catalyst (MoS_(2)-Fe_(x)) prepared in a simple way with highly dispersed iron to provide more active sites. MoS_(2)-Fe_(x) was proved to possess selectivity for singlet oxygen (^(1)O_(2)) in effectively degrading sulfadiazine with a wide pH adaptability (4.0~10.0). Importantly, the mechanism of the interaction between H_(2)O_(2) and MoS_(2) on the Fenton reaction activity was revealed through the combination of experiment and density functional theory (DFT) calculations. Compared to the traditional “a large amount for one time” feeding way of H_(2)O_(2), the “small amount for multiple times” of H_(2)O_(2) feeding way can increase the degradation rate of sulfadiazine from 36.9% to 91.1% in the MoS_(2)-Fe_(x) heterogeneous Fenton system. It is demonstrated that the “small amount for multiple times” of H_(2)O_(2) feeding way can reduce the side reaction of decomposition of H_(2)O_(2) by MoS_(2) and effectively improve the utilization rate of H_(2)O_(2) and the stability of MoS_(2)-Fe_(x). Compared with Fe_(2)O_(3)^(-)based Fenton system, MoS_(2)-Fe_(x) can significantly save the amount of H_(2)O_(2). Compared with nano-iron powder, the formation of iron sludge in MoS_(2)-Fe_(x) system was significantly reduced. Furthermore, long-term degradation test showed that the MoS_(2)-Fe75/H_(2)O_(2) system could maintain the effectiveness of degrading organic pollutants for 10 days (or even longer). This study has a guiding significance for the large-scale treatment of industrial wastewater by improved Fenton technology in the future.

Enhanced methanation stability of nano-sized MoS2 catalysts by adding Al2O3

A series of unsupported MoS2 catalysts with or without Al2O3 modification was prepared using a modified thermal decomposition approach. The catalysts were tested for the methanation of carbon monoxide and the optimum one has 25.6wt-% Al2O3 content. The catalysts were characterized by nitrogen adsorption measurement, X-ray diffraction and transmission electron microscopy. The results show that adding appropriate amount of Al2O3 increases the dispersion of MoS2, and the increased interaction force between MoS2 and Al2O3 can inhibit the sintering of active MoS2 to some extent.

Enhanced Li^＋ storage properties of few-layered MoS2-C composite microspheres embedded with Si nanopowder

A few-layered MoS2-C composite material is studied as a supporting material for silicon nanopowder. Microspheres of the few-layered MoS2-C composite embedded with 30 wt.% Si nanopowder are prepared by one-pot spray pyrolysis. The Si nanopowder particles with high capacity are completely surrounded by the few-layered MoS2-C composite matrix. The discharge capacities of the MoS2-C composite microspheres with and without 30 wt.% Si nanopowder after 100 cycles are 1,020 and 718 mAh·g^-1 at a current density of 1,000 mA·g^-1 respectively. The spherical morphology of the MoS2-C composite microspheres embedded with Si nanopowder is preserved even after 100 cycles because of their high structural stability during cycling. The MoS2-C composite layer prevents the formation of unstable solid-electrolyte interface （SEI） layers on the Si nanopowder. Furthermore, as the MoS2-C composite matrix exhibits high capacity and excellent cycling performance, these characteristics are also reflected in the MoS2-C composite microspheres embedded with 30 wt.% Si nanopowder.