Facet effect on the reconstructed Cu-catalyzed electrochemical hydrogenation of 5-hydroxymethylfurfural(HMF) towards 2,5-bis(hydroxymethy)furan (BHMF)

The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.

Electrochemical hydrogen storage characteristics of nanocrystalline and amorphous Mg_2Ni-type alloys prepared by melt-spinning

The nanocrystalline and amorphous Mg2Ni-type alloys with nominal compositions of Mg2Ni1-xMnx （x=0, 0.1, 0.2, 0.3, 0.4） were synthesized by melt-spinning technique. The spun alloy ribbons with a continuous length, a thickness of about 30 μm and a width of about 25 mm are obtained. The structures of the as-spun alloy ribbons were characterized by XRD and HRTEM. The electrochemical hydrogen storage characteristics of the as-spun alloy ribbons were measured by an automatic galvanostatic system. The electrochemical impedance spectrums （EIS） were plotted by an electrochemical workstation. The hydrogen diffusion coefficients （D） in the alloys were calculated by virtue of potential-step measurement. The results show that all the as-spun （x=0） alloys hold a typical nanocrystalline structure, whereas the as-spun （x=0.4） alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg2Ni-type alloy. The substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn substitution from 0 to 0.4, the discharge capacity of the as-spun （20 m/s） alloy increases from 96.5 to 265.3 mA·h/g, and its capacity retaining rate （S20） at the 20th cycle increases from 31.3% to 70.2%. Furthermore, the high rate dischargeability （HRD）, electrochemical impedance spectrum and potential-step measurements all indicate that the electrochemical kinetics of the alloy electrodes first increases then decreases with raising the amount of Mn substitution.

Electrochemical hydrogen compression and purification versus competing technologies: Part Ⅱ. Challenges in electrocatalysis

Hydrogen will be at the basis of the World’s energy policy in forthcoming decades, owing to its decarbonized nature, at least when produced from renewables. For now, hydrogen is still essentially produced from fossil feedstock(and to a minor extent from biomass);in consequence the present hydrogen gas on the market is containing non-negligible amounts of impurities that prevent its immediate usage in specialty chemistry or as an energy carrier in fuel cells, e.g. in transportation applications(cars, buses, trains, boats, etc.) that gradually spread on the planet. For these purposes, hydrogen must be of sufficient purity but also sufficiently compressed(at high pressures, typically 70 MPa), rendering purification and compression steps unavoidable in the hydrogen cycle. As shown in the first part of this contribution "Electrochemical hydrogen compression and purification versus competing technologies: Part I. pros and cons", electrochemical hydrogen compressors(EHCs), which enable both hydrogen purification and compression, exhibit many theoretical(thermodynamic) and practical(kinetics) advantages over their mechanical counterparts. However, in order to be competitive, EHCs must operate in very intensive conditions(high current density and low cell voltage) that can only be reached if their core materials, e.g. the membrane and the electrodes/electrocatalysts, are optimized. This contribution will particularly focus on the properties electrocatalysts must exhibit to be used in EHCs: they shall promote(very) fast hydrogen oxidation reaction(HOR) in presence of impurities, which implies that they are(very) tolerant to poisons as well. This consists of a prerequisite for the operation of the anode of an EHC used for the purification-compression of hydrogen, and the materials developed for poison-tolerance in the vast literature on low-temperature fuel cells, may not always satisfy these two criteria, as this contribution will review.

Electrochemical hydrogen compression and purification versus competing technologies: Part Ⅰ. Pros and cons

It is undisputed that hydrogen will play a great role in our future energetic mix, because it enables the storage of renewable electricity(power-to-H2) and the reversible conversion into electricity in fuel cell, not to speak of its wide use in the(petro)chemical industry. Whereas in these applications, pure hydrogen is required, today’s hydrogen production is still largely based on fossil fuels and can therefore not be considered pure. Therefore, purification of hydrogen is mandatory, at a large scale. In addition, hydrogen being the lightest gas, its volumetric energy content is well-below its competing fuels, unless it is compressed at high pressures(typically 70 MPa), making compression unavoidable as well. This contribution will detail the means available today for both purification and for compression of hydrogen. It will show that among the available technologies, the electrochemical hydrogen compressor(EHC), which also enables hydrogen purification, has numerous advantages compared to the classical technologies currently used at the industrial scale. EHC has their thermodynamic and operational advantages, but also their ease of use. However, the deployment of EHCs will be viable only if they reach sufficient performances, which implies some specifications that their base materials should stick to. The present contribution will detail these specifications.

Effect of Ni,Fe and Fe-Ni alloy catalysts on the synthesis of metal contained carbon nano-onions and studies of their electrochemical hydrogen storage properties

Three types of carbon nano-onions（CNOs） including Ni@CNOs.Fe3C@CNOs and Fe0.64Ni0.36@CNOs nanoparticles have been synthesized by catalytic decomposition of methane at 850 ℃ using nickel,iron and iron-nickel alloy catalysts.Comparative and systematic studies have been carried out on the morphology,structural characteristics and graphitic crystallinity of these CNOs products.Furthermore,the electrochemical hydrogen storage properties of three types of CNOs have been investigated.Measurements show that the Ni@CNOs have the highest discharge capacity of 387.2 mAh/g,coiTesponding to a hydrogen storage of 1.42%.This comparison study shows the advantages of each catalyst in the growth of CNOs.enabling the controllable synthesis and tuning the properties of CNOs by mediating different metals and their alloy for using in the fuel cell system.

Improved electrochemical hydrogen storage properties of Mg-Y thin films as a function of substrate temperature

Pd-capped Mg78Y22 thin films have been prepared by direct current magnetron co-sputtering system at different substrate temperatures and their electrochemical hydrogen storage properties have been investigated.It is found that rising substrate temperature to 60 ℃ can coarsen the surface of thin film,thus facilitating the diffusion of hydrogen atoms and then enhancing its discharge capacity to 1725 mAh·g-1.Simultaneously,the cyclic stability is effectively improved due to the increased adhesion force between film and substrate as a function of temperature.In addition,the specimen exhibits a very long and flat discharge plateau at about —0.67 V,at which nearly 60%of capacity is maintained.The property is favorable for the application in metal hydride/nickel secondary batteries.The results indicate that rising optimal substrate temperature has a beneficial effect on the electrochemical hydrogen storage of Mg-Y thin films.

Towards electrochemical hydrogen storage in liquid organic hydrogen carriers via proton-coupled electron transfers

Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO_(2).A possible solution for the transport of H_(2)in a safe and low-cost way is in the form of liquid organic hydrogen carriers(LOHCs).As an alternative to loading LOHC with H_(2)via a two-step procedure involving preliminary electrolytic production of H_(2)and subsequent chemical hydrogenation of the LOHC,we explore here the possibility of electrochemical hydrogen storage(EHS)via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the LOHC(R)via a protoncoupled electron transfer(PCET)reaction:2nH^(+)+2ne^(-)+Rox■n H_(2)^(0)Rred.We chose 9-fluorenone/fluorenol(Fnone/Fnol)conversion as such a model PCET reaction.The electrochemical activation of Fnone via two sequential electron transfers was monitored with in-situ and operando spectroscopies in absence and in presence of different alcohols as proton donors of different reactivity,which enabled us to both quantify and get the mechanistic insight on PCET.The possibility of hydrogen extraction from the loaded carrier molecule was illustrated by chemical activation.

A NEW INTELLIGENT AMPEROMETRIC TYPE OF ELECTROCHEMICAL HYDROGEN PROBE

A new intelligent amperometric type of electrochemical hydrogen probe to measure hydrogen atom permeation rate in the metals was devised and developed. Combined with MCS51 single slice computer system, specially programmed software was designed for data sampling, logging, storing, processing, result judgment and data output controlling. The probe is portable and can be used in both lab and in site automatically.

Electrochemical Hydrogen Absorbing/Desorbing Behavior of Double Phase Mg-Ni Alloy

The electrochemical performance of double phase Mg Ni alloy was characterized at 25°C and 70°C, in order to evaluate briefly its utility as negative electrode materials in nickel metal hydride batteries. The results show that the electrochemical capacity of double phase Mg Ni alloy is rarely low at 25°C, but increased rapidly when the temperature is enhanced, and the double phase Mg Ni alloy has its maximum capacity at the first discharge cycle, but the capacity degrades rapidly with cycling number.

Effect of Nitrogen and Sulfur Co‑Doped Graphene on the Electrochemical Hydrogen Storage Performance of Co_(0.9)Cu_(0.1)Si Alloy

Co_(0.9)Cu_(0.1)Si alloy was prepared by mechanical alloying method.Nitrogen-doped graphene(NG)and nitrogen–sulfur codoped graphene(NSG)were prepared by hydrothermal method.5 wt%graphene oxide,NG and NSG were doped into Co_(0.9)Cu_(0.1)Si alloy,respectively,by ball milling to improve the electrochemical hydrogen storage performance of the composite material.X-ray diffraction and scanning electron microscopy were used to characterize the structure and morphology of the composite material,and the LAND battery test system and three-electrode battery system were used to test the electrochemical performance of the composite material.The composite material showed better discharge capacity and better cycle stability than the pristine alloy.In addition,in order to study the optimal ratio of NSG,3%,5%,7%and 10%of NSG were doped into Co_(0.9)Cu_(0.1)Si alloy,respectively.Co_(0.9)Cu_(0.1)Si alloy doped with 5%NSG had the best performance among all the samples.The best discharge capacity was 580.1 mAh/g,and its highest capacity retention rate was 64.1%.The improvement in electrochemical hydrogen storage performance can be attributed to two aspects.On the one hand,the electrocatalytic performance of graphene is improved by co-doping nitrogen and sulfur,on the other hand,graphene has excellent electrical conductivity.

Structure and electrochemical hydrogen storage characteristics of Ce-Mg-Ni-based alloys synthesized by mechanical milling

The substituting Mg with Ni and milling as-cast alloy with Ni were adopted to obtain nanocrystalline/amorphous CeMgnNi＋x wt.%Ni（x=100,200） alloys and promote the electrochemical hydrogen storage performances of CeMg_（12）-type alloys.Analyzing the structural features of the alloys provided a mechanism for ameliorating the electrochemical hydrogen storage properties.The electrochemical tests demonstrated that all the alloys just needed one cycle to be activated.Rising Ni proportion had an obvious role on charge-discharge reaction.The discharge capacities of the as-milled（60 h） alloys increased sharply from 182.0 mAh/gfor x=100 alloy to 1010.2 mAh/gfor x=200 alloy at current density of 60 mAh/g.Furthermore,milling time largely determined the performances of electrochemical reaction.The discharge capacity continued to grow along with prolonging milling time,while the cycle stability obviously decreased for x=100 alloy,and first declined and then augmented for the x=200 alloy with milling time extending.In addition,there was an optimal value with milling time varying for the high rate discharge abilities（HRD）,which was 80.3%for x=100 alloys and 86.73%for x=200,respectively.

Electrochemical hydrogen storage performances of the nanocrystalline and amorphous(Mg_(24)Ni_(10)Cu_2)_(100–x)Nd_x(x=0–20) alloys applied to Ni-MH battery

Melt spinning technology was used to prepare the Mg2 Ni-type（Mg24 Ni10 Cu2）100–x Ndx（x=0,5,10,15,20） alloys in order to obtain a nanocrystalline and amorphous structure.The effects of Nd content and spinning rate on the structures and electrochemical hydrogen storage performances of the alloys were investigated.The structure characterizations of X-ray diffraction（XRD）,transmission electron microscopy（TEM） and scanning electron microscopy（SEM） linked with energy dispersive spectroscopy（EDS） revealed that the as-spun Nd-free alloy displayed an entire nanocrystalline structure,whereas the as-spun Nd-added alloys held a nanocrystalline and amorphous structure and the degree of amorphization visibly increased with the rising of Nd content and spinning rate,suggesting that the addition of Nd facilitated the glass forming of the Mg2 Ni-type alloy.The electrochemical measurements indicated that the addition of Nd and melt spinning improved the electrochemical hydrogen storage performances of the alloys significantly.The discharge capacities of the as-cast and spun alloys exhibited maximum values when Nd content was x=10,which were 86.4,200.5,266.3,402.5 and 452.8 mAh/g corresponding to the spinning rate of 0（As-cast was defined as the spinning rate of 0 m/s）,10,20,30 and 40 m/s,respectively.The cycle stability（S20,the capacity maintain rate at 20thcycle） of the as-cast alloy always rose with the increasing of Nd content,and those of the as-spun alloys exhibited the maximum values for Nd content x=10,which were 77.9%,83.4% 89.2% and 89.7%,corresponding to the spinning rate of 10,20,30 and 40 m/s,respectively.

Catalytic hydrogenation performance of ZIF-8 carbide for electrochemical reduction of carbon dioxide

The conversion of CO_(2) electrocatalytic hydrogenation into energy-rich fuel is considered to be the most effective way to carbon recycle.Nitrogen-doping carbonized ZIF-8 is proposed as carrier of the earth-rich Sn catalyst to overcome the limit of electron transfer and CO_(2) adsorption capacity of Sn.Hierarchically porous structure of Sn doped carbonized ZIF-8 is controlled by hydrothermal and carbonization conditions,which induces much higher specific surface area than that of the commercial Sn nanoparticle(1003.174 vs.7.410 m^(2)·g^(-1)).The shift of nitrogen peaks in X-ray Photoelectron Spectroscopy spectra indicates interaction between ZIF-8 and Sn,which induces the shift of electron cloud from Sn to the chemical nitrogen to enhance conductivity and regulate electron transfer from catalyst to CO_(2).Lower mass transfer resistance and Warburg resistance are investigated through EIS,which significantly improves the catalytic activity for CO_(2) reduction reaction(CO_(2)RR).Onset potential of the reaction is reduced from-0.74 V to less than-0.54 V vs.RHE.The total Faraday efficiency of HCOOH and CO reaches 68.9%at-1.14 V vs.RHE,which is much higher than that of the commercial Sn(45.0%)and some other Sn-based catalyst reported in the literature.

Electrochemical hydrogenation of mixed-phase TiO2 nanotube arrays enables remarkably enhanced photoelectrochemical water splitting performance

We first report that photoelectrochemical （PEC） performance of electrochemically hydrogenated TiO2 nanotube arrays （TNTAs） as high-efficiency photoanodes for solar water splitting could be well tuned by designing and adjusting the phase structure and composition of TNTAs. Among various TNTAs annealed at different temperature ranging from 300 to 700℃, well-crystallized single anatase （A） phase TNTAs-400 photoanode shows the best photoresponse properties and PEC performance due to the favor- able crystallinity, grain size and tubular structures. After electrochemical hydrogenation （EH）. anatase- rutile （A-R） mixed phase EH-TNTAs-600 photoanode exhibits the highest photoactivity and PEC perfor- mance for solar water splitting. Under simulated solar illumination, EH-TNTAs-600 achieves the best photoconversion efficiency of up to 1.52% and maximum H2 generation rate of 40.4 ~mol h i cm-2, our- stripping other EH-TNTAs photoanodes. Systematic studies reveal that the signigicantly enhanced PEC performance for A-R mixed phaes EH-TNTAs-600 photoanode could be attributed to the synergy of A-R mixed phases and intentionally introduced Ti3~ （oxygen vacancies） which enhances the photoactivity over both UV and visible-light regions, and boosts both charge separation and transfer efficiencies. These findings provide new insight and guidelines for the construction of highly efficient TiO2-based devices for the application of solar water splitting.

ELECTROCHEMICAL PROPERTIES OF THE HYDROGEN ABSORPTION OF AMORPHOUS Ml－Ni ALLOY FILMS

The amorphous Ml-Ni films were prepared by means of ion beam sputtering the electrochemical hydrogen storage,discharge ability and durability of amorphous film electrodes are investigated,The results show that the maximum capacities of the amorphous MlNi_(1.79),MlNi_(2.52),and MlNi_(3.44) samples are 90,100 and 142 mAh/g,respectively,and the MlNi_(3.44) amorphous film does not off and disintegrate into fine particles a fier more than 580 cycles.

Research Surveys of Electrochemical Sensors for in-situ Determining Hydrogen in Steels

The principle, construction and application of two types of electrochemical sensors-amperometric and potentiometric are surveyed. Both types of sensors are very sensitive to changes in temperature. The accuracy of hydrogen measurement depends on both the precision of sensors developed and the reliable technique of installation and security of sensors. The two types of sensors have been used for in-situ determining hydrogen permeated in steels owing to a corrosive reaction, a hydrogen gas circumstance at elevated temperatures and high pressure or also a pretreatment process such as pickling and plating process, etc.

Electrocatalytic hydrogen peroxide formation on mesoporous non-metal nitrogen-doped carbon catalyst

Direct electrochemical formation of hydrogen peroxide（H2O2） from pure O2 and H2on cheap metal-free earth abundant catalysts has emerged as the highest atom-efficient and environmentally friendly reaction pathway and is therefore of great interest from an academic and industrial point of view. Very recently,novel metal-free mesoporous nitrogen-doped carbon catalysts have attracted large attention due to the unique reactivity and selectivity for the electrochemical hydrogen peroxide formation [1–3]. In this work,we provide deeper insights into the electrocatalytic activity, selectivity and durability of novel metal-free mesoporous nitrogen-doped carbon catalyst for the peroxide formation with a particular emphasis on the influence of experimental reaction parameters such as p H value and electrode potential for three different electrolytes. We used two independent approaches for the investigation of electrochemical hydrogen peroxide formation, namely rotating ring-disk electrode（RRDE） technique and photometric UV–VIS technique. Our electrochemical and photometric results clearly revealed a considerable peroxide formation activity as well as high catalyst durability for the metal-free nitrogen-doped carbon catalyst material in both acidic as well as neutral medium at the same electrode potential under ambient temperature and pressure. In addition, the obtained electrochemical reactivity and selectivity indicate that the mechanisms for the electrochemical formation and decomposition of peroxide are strongly dependent on the p H value and electrode potential.

Corrosion Rate of Hydrogenation to C110 Casing in High H_2S Environment

The corrosion behavior of C110 bushing at high temperature and high pressure with a high H2S / CO2 was studied, and a basis for the materials selection of sour gas well bushing was provided in H2S, CO2 and saline coexisting environment. Under acidic condiction, hydrogen atoms greatly entered into the material and caused the material properties changed. Weight loss method was used to study the corrosion rate of hydrogen charging samples and original untreated samples in simulated oil field environment. PAR2273 electrochemical workstation was used to examine the electrochemical performance of samples untreated, hydrogen charging after reacting in autoclave. The corrosion product film was observed through SEM. The experimental results show that sample with hydrogen charging has a much more obvious partial corrosion and pitting corrosion than the untreated blank sample even the downhole corrosion speed of bushing is increased after being used for a period of time. Polarization curve shows the corrosion tendency is the same between sample with or without hydrogen charging and corrosion tendency is reduced by corrosion product film. A layer of dense product film formed on the surface of samples provides a certain protective effect to the matrix, but cracked holes which will accelerate partial corrosion of the sample were also observed.

Heterophase junction engineering-induced Co spin-state modulation of CoSe_(2) for large-current hydrogen evolution reaction

Efficient electrocatalysts are vital to large-current hydrogen production in commercial water splitting for green energy generation.Herein,a novel heterophase engineering strategy is described to produce polymorphic CoSe_(2)electrocatalysts.The composition of the electrocatalysts consisting of both cubic CoSe_(2)(c-CoSe_(2))and orthorhombic CoSe_(2)(o-CoSe_(2))phases can be controlled precisely.Our results demonstrate that junction-induced spin-state modulation of Co atoms enhances the adsorption of intermediates and accelerates charge transfer resulting in superior large-current hydrogen evolution reaction(HER)properties.Specifically,the CoSe_(2)based heterophase catalyst with the optimal c-CoSe_(2)content requires an overpotential of merely 240 mV to achieve 1,000 mA·cm^(-2)as well as a Tafel slope of 50.4 mV·dec^(-1).Furthermore,the electrocatalyst can maintain a large current density of 1,500 mA·cm^(-2)for over 320 h without decay.The results reveal the advantages and potential of heterophase junction engineering pertaining to design and fabrication of low-cost transition metal catalysts for large-current water splitting.

Gaseous sorption and electrochemical properties of rare-earth hydrogen storage alloys and their representative applications： A review of recent progress

The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.