Efficient C-N coupling in electrocatalytic urea generation on copper carbonate hydroxide electrocatalysts

Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.

Coupling and Long-term Change Characteristics of Forest Carbon Sink and Forestry Economic Development in China

[Objectives]To analyze the changes in of forest carbon sink and forestry economic development,provide reference for relevant management decisions,ecological governance and resource and environment management,and promote the development of green low-carbon economy in China.[Methods]Based on the data of six forest resource inventories from 1989 to 2018 and related studies,the comprehensive evaluation model of forest carbon sink and forestry economic development,the coupling degree model of forest carbon sink and forestry economic development,and the coupling coordination degree model of forest carbon sink and forestry economic development were adopted.The coupling degree of forest carbon sink and forestry economic development from 1992 to 2018 was analyzed.Stepwise regression and ARIMA model were used to analyze the influencing factors and lagging characteristics of forest carbon sink.The coupling degree between forest carbon sink and forestry economic development in China from 2019 to 2030 was predicted by autoregression and ADF test.The coupling between forest carbon sink and forestry economic development in China and its long-term change characteristics were also discussed in this study.[Results](i)The investment of ecological construction and protection,the actual investment of forestry key ecological projects,GDP and the import of forest products had a significant impact on forest resources carbon stock.The total output value of forestry industry,the actually completed investment of forestry key ecological projects and the export volume of forest products had a significant impact on the forest carbon sink,and the actually completed investment of forestry key ecological projects has the greatest impact on the two.(ii)The impact of actually completed investment of forestry key ecological projects had a lag of 2 years on the forest resources carbon stock and a lag of 1 year on the forest carbon sink.When investing in forest carbon sink,it is necessary to make a good plan in advance,and do a good job in forest resources management and time optimization.(iii)From 1992 to 2018,the coupling degree of forest resources carbon stock,forest carbon sink and long-term development of forestry economy in China was gradually increasing.Although there were some fluctuations in the middle time,the coupling degree of forest resources carbon stock and the long-term development of forestry economy increased by 9.24%annually,and the degree of coupling coordination increased from"serious imbalance"in 1992 to"high-quality coordination"in 2018.From 1993 to 2018,the coupling degree of forest carbon sink and long-term development of forestry economy increased by 9.63%annually,slightly faster than the coupling coordination degree of forest resources carbon stock and long-term development of forestry economy.The coordination level also rose from level 2 in 1993 to level 10 in 2018.(iv)The prediction shows that the coupling coordination degree of forest resources carbon stock,forest carbon sink and the long-term development of forestry economy would increase from 2019 to 2030.The coupling coordination degree(D)values of both were close to 1,the coordination level was also 10 for a long time,and the degree of coupling coordination was also maintained at the"high-quality coordination"level for a long time.[Conclusions]Forest has multiple benefits of society,economy and ecology,and forest carbon sink is only a benefit output.The long-term coupling analysis of forest carbon sink and forestry economic development is a key point to multiple benefit analysis.The analysis shows that the spillover effect and co-evolution effect of forest carbon sink in China are significant.From 1992 to 2018,the coupling coordination degree of forest carbon sink and forestry economic development was gradually rising.The prediction analysis also indicate that the coupling coordination degree between the forest carbon sink and the long-term development of forestry economy will remain at the level of"high-quality coordination"for a long time from 2019 to 2030.Therefore,improving the level of forest management and maintaining the current trend of increasing forest resources are the key to achieving the goal of carbon peaking and carbon neutrality in China.

In situ formation of multiple catalysts for enhancing the hydrogen storage of MgH_(2) by adding porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres

MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).

Photothermal catalytic C-C coupling to ethylene from CO_(2) with high efficiency by synergistic cooperation of oxygen vacancy and half-metallic WTe_(2)

Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.

Unveiling the chemistry behind the electrolytic production of hydrogen peroxide by oxygenated carbon

Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.

A thermodynamic view on the in-situ carbon dioxide reduction by biomass-derived hydrogen during calcium carbonate decomposition

In the carbonate industry,deep decarbonization strategies are necessary to effectively remediate CO_(2).These strategies mainly include both sustainable energy supplies and the conversion of CO_(2)in downstream processes.This study developed a coupled process of biomass chemical looping H2 production and reductive calcination of CaCO_(3).Firstly,a mass and energy balance of the coupled process was established in Aspen Plus.Following this,process optimization and energy integration were implemented to provide optimized operation conditions.Lastly,a life cycle assessment was carried out to assess the carbon footprint of the coupled process.Results reveal that the decomposition temperature of CaCO_(3)in an H_(2)atmosphere can be reduced to 780℃(generally around 900℃),and the conversion of CO_(2)from CaCO_(3)decomposition reached 81.33%with an H2:CO ratio of 2.49 in gaseous products.By optimizing systemic energy through heat integration,an energy efficiency of 86.30%was achieved.Additionally,the carbon footprint analysis revealed that the process with energy integration had a low global warming potential(GWP)of-2.624 kg·kg^(-1)(CO_(2)/CaO).Conclusively,this work performed a systematic analysis of introducing biomass-derived H_(2)into CaCO_(3)calcination and demonstrated the positive role of reductive calcination using green H_(2)in mitigating CO_(2)emissions within the carbonate industry.

Accelerating H^(*)desorption of hollow Mo_(2)C nanoreactor via in-situ grown carbon dots for electrocatalytic hydrogen evolution

Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.

Simulation study of supercritical carbon dioxide jet fracturing for carbonate geothermal reservoir based on fluid-thermo-mechanical coupling model

Geothermal energy is a kind of renewable,sustainable and clean energy resource.Geothermal energy is abundant in carbonate reservoirs.However,low matrix permeability limits its exploitation.The super-critical carbon dioxide(SC-CO_(2))jet fracturing is expected to efficiently stimulate the carbonate geothermal reservoirs and achieve the storage of CO_(2) simultaneously.In this paper,we established a transient seepage and fluid-thermo-mechanical coupled model to analyze the impact performance of sc-CO_(2) jet fracturing.The mesh-based parallel code coupling interface was employed to couple the fluid and solid domains by exchanging the data through the mesh interface.The physical properties change of sC-CO_(2) with temperature were considered in the numerical model.Results showed that SC-CO_(2) jet frac-turing is superior to water-jet fracturing with respect to jetting velocity,particle trajectory and pene-trability.Besides,stress distribution on the carbonate rock showed that the tensile and shear failure would more easily occur by SC-CO_(2) jet than that by water jet.Moreover,pressure and temperature control the jet field and seepage field of sC-CO_(2) simultaneously.Increasing the jet temperature can effectively enhance the impingement effect and seepage process by decreasing the viscosity and density of SC-CO_(2).The key findings are expected to provide a theoretical basis and design reference for applying SC-CO_(2) jet fracturing in carbonate geothermal reservoirs.

Optimal Operation Strategy of Electricity-Hydrogen Regional Energy System under Carbon-Electricity Market Trading

Given the“double carbon”objective and the drive toward low-carbon power,investigating the integration and interaction within the carbon-electricity market can enhance renewable energy utilization and facilitate energy conservation and emission reduction endeavors.However,further research is necessary to explore operational optimization methods for establishing a regional energy system using Power-to-Hydrogen(P2H)technology,focusing on participating in combined carbon-electricity market transactions.This study introduces an innovative Electro-Hydrogen Regional Energy System(EHRES)in this context.This system integrates renewable energy sources,a P2H system,cogeneration units,and energy storage devices.The core purpose of this integration is to optimize renewable energy utilization and minimize carbon emissions.This study aims to formulate an optimal operational strategy for EHRES,enabling its dynamic engagement in carbon-electricity market transactions.The initial phase entails establishing the technological framework of the electricity-hydrogen coupling system integrated with P2H.Subsequently,an analysis is conducted to examine the operational mode of EHRES as it participates in carbon-electricity market transactions.Additionally,the system scheduling model includes a stepped carbon trading price mechanism,considering the combined heat and power generation characteristics of the Hydrogen Fuel Cell(HFC).This facilitates the establishment of an optimal operational model for EHRES,aiming to minimize the overall operating cost.The simulation example illustrates that the coordinated operation of EHRES in carbon-electricity market transactions holds the potential to improve renewable energy utilization and reduce the overall system cost.This result carries significant implications for attaining advantages in both low-carbon and economic aspects.

Data-driven source-load robust optimal scheduling of integrated energy production unit including hydrogen energy coupling

A robust low-carbon economic optimal scheduling method that considers source-load uncertainty and hydrogen energy utilization is developed.The proposed method overcomes the challenge of source-load random fluctuations in integrated energy systems(IESs)in the operation scheduling problem of integrated energy production units(IEPUs).First,to solve the problem of inaccurate prediction of renewable energy output,an improved robust kernel density estimation method is proposed to construct a data-driven uncertainty output set of renewable energy sources statistically and build a typical scenario of load uncertainty using stochastic scenario reduction.Subsequently,to resolve the problem of insufficient utilization of hydrogen energy in existing IEPUs,a robust low-carbon economic optimal scheduling model of the source-load interaction of an IES with a hydrogen energy system is established.The system considers the further utilization of energy using hydrogen energy coupling equipment(such as hydrogen storage devices and fuel cells)and the comprehensive demand response of load-side schedulable resources.The simulation results show that the proposed robust stochastic optimization model driven by data can effectively reduce carbon dioxide emissions,improve the source-load interaction of the IES,realize the efficient use of hydrogen energy,and improve system robustness.

Revealing sodium storage mechanism of hard carbon anodes through in-situ investigation of mechano-electrochemical coupling behavior

Hard carbon(HC)is considered a promising anode material for sodium-ion batteries due to its relatively low price and high specific capacity.However,HC still suffers from unclear reaction mechanisms and unsatisfactory cycling stability.The study of mechano-electrochemical coupling behavior by in-situ measurement techniques is expected to understand the sodium storage and degradation mechanisms.In this paper,the strain and stress evolution of HC anodes at different sodiation/desodiation depths and cycles are investigated by combining electrochemical methods,digital image correlation,and theoretical equations.The observation by monitoring the in-situ strain evolution during the redox process supports the“adsorption-intercalation/filling”mechanism in reduction and the“de-filling/de-intercalation-deso rption”mechanism in oxidation.Further studies have demonstrated that the strain and stress of the electrode show periodic changes accompanied by a continuous accumulation of residual stress during cycles,explaining the capacity degradation mechanism of HC from a mechanical perspective.In addition,when the higher current density is applied,the electrodes experience greater strain and stress associated with the Na+insertion rate.This work clarifies the Na-storage mechanism and the mechano-electrochemical coupling mechanism of HC anodes by in-situ strain measurement,which helps optimize and design the anode materials of sodium-ion batteries from the perspective of interface microstructure and multi-field coupling,such as in situ integrated interface structure design.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

Coupling dehydrogenation of isobutane in the presence of carbon dioxide over chromium oxide supported on active carbon

The dehydrogenation of isobutane （IB） to produce isobutene coupled with reverse water gas shift in the presence of carbon dioxide was investigated over the catalyst Cr2O3 supported on active carbon （Cr2O3/AC）. The results illustrated that isobutane conversion and isobutene yield can be enhanced through the reaction coupling in the presence of carbon dioxide. Moreover, carbon dioxide can partially eliminate carbonaceous deposition on the catalyst and keep the active phase （Cr2O3）, which are then helpful to alleviate the catalyst deactivation.

Minimizing carbon deposition in plasma-induced methane coupling with structured hydrogenation catalysts

The effect of temperature and hydrogen addition on undesired carbonaceous deposit formation during methane coupling was studied in DBD-plasma catalytic-wall reactors with Pd/Al2 O3, using electrical power to drive the reaction.Experiments with thin catalyst layers allowed comparison of the performance of empty reactors and catalytic wall reactors without significantly influencing the plasma properties.The product distribution varies strongly in the temperature window between 25 and 200℃Minimal formation of deposits is found at an optimal temperature around 75℃ in the catalytic-wall reactors.The selectivity to deposits was c.a.10% with only 9 mg of catalyst loading instead of 45% in the blank reactor,while decreasing methane conversion only mildly.Co-feeding H2 to an empty reactor causes a similar decrease in selectivity to deposits,but in this case methane conversion also decreased significantly.Suppression of deposits formation in the catalytic-wall reactor at 75℃ is due to catalytic hydrogenation of mainly acetylene to ethylene.In the empty reactor,H2 co-feed decreases conversion but does not change the product distribution.The catalytic-wall reactors can be regenerated with H2-plasma at room temperature,which produces more added-value hydrocarbons.

Co-Ru alloy nanoparticles decorated onto two-dimensional nitrogen doped carbon nanosheets towards hydrogen/oxygen evolution reaction and oxygen reduction reaction

Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.

MoNi_(4)-NiO heterojunction encapsulated in lignin-derived carbon for efficient hydrogen evolution reaction

Molybdenum nickel alloy has been proved to be an efficient noble-metal-free catalyst for hydrogen evolution reaction(HER) in alkaline medium, but its electrocatalytic activity and stability need to be further improved to meet industrial requirements. In this study, carboxymethylated enzymatic hydrolysis lignin(EHL) was used as a biomacromolecule frame to coordinate with transition metal ions and reduced by pyrolysis to obtain the MoNi_(4)-NiO heterojunction(MoNi_(4)-NiO/C). The oblate sphere structure of MoNi_(4)-NiO/C exposed a large catalytic active surface to the electrolyte. As a result, the hydrogen evolution reaction of MoNi_(4)-NiO/C displayed a low overpotentials of 41 mV to achieve 10 mA cm-2and excellent stability of 100 h at 100 mA cm^(-2)in 1 mol L^(-1)KOH, which was superior to that of commercial Pt/C. Lignin assisted the formation of NiO to construct the MoNi_(4)-NiO interface and MoNi_(4)-NiO heterojunction structure, which reduced the energy barrier by forming a more favorable transition states and then promoted the formation of adsorbed hydrogen at the heterojunction interface through water dissociation in alkaline media, leading to the rapid reaction kinetics. This work provided an effective strategy for improving the electrocatalytic performance of noble-metal-free electrocatalysts encapsulated by lignin-derived carbon.

Hydrogen for a Net-Zero Carbon World

1.Why hydrogen?The concept of the“hydrogen economy”was first coined by Prof.John Bockris during a talk he gave in 1970 at the General Motors Technical Center.Bockris’s talk introduced the vision of a world economy in which energy was carried in the form of hydrogen.

Carbon Nitride Quantum Dots:A Novel Fluorescent Probe for Non-Enzymatic Hydrogen Peroxide and Mercury Detection

The mercury species in the ocean(MeHg,Hg^(2+))will be enriched in marine organisms and threaten human health through the food chain.While the excessive H_(2)O_(2)in the metabolic process will produce hydroxyl radicals and accelerate the aging of human cells,causing a series of diseases.Hence,the cost-effective and rapid detection of mercury and H_(2)O_(2)is of urgent requirement and significance.Here,we synthesized emerging graphitic carbon nitride quantum dots(g-CNQDs)with high fluorescence quantum yield(FLQY)of 42.69%via a bottom-up strategy by a facile one-step hydrothermal method.The g-CNQDs can detect the H_(2)O_(2)and Hg^(2+)through the fluorescence quenching effect between g-CNQDs and detected substances.With the presence of KI,g-CNQDs show concentration-dependent fluorescence toward H_(2)O_(2),with a wide detection range of 1–1000μmolL^(-1)and a low detection limit of 0.23μmolL^(-1).The g-CNQDs also show sensitivity toward Hg^(2+)with a detection range of 0–0.1μmolL^(-1)and a detection limit of 0.038μmolL^(-1).This dual-function detection of g-CNQDs has better practical application capability compared to other quantum dot detection.This study may provide a new strategy for g-CNQDs preparation and construct a fluorescence probe that can be used in various systems involving H_(2)O_(2)and Hg^(2+),providing better support for future bifunctional or multifunction studies.

Electrochemical hydrogen evolution efficiently boosted by interfacial charge redistribution in Ru/MoSe_(2) embedded mesoporous hollow carbon spheres

The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.

Carbon Doping Triggered Efficient Electrochemical Hydrogen Evolution of Cross-Linked Porous Ru-MoO_(2) Via Solid-Phase Reaction Strategy

The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).