Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin

This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.

Possibilities for the synthesis of superheavy element Z=121 in fusion reactions

Based on the dinuclear system model,the calculated evaporation residue cross sections matched well with the current experimental results.The synthesis of superheavy elements Z=121 was systematically studied through combinations of stable projectiles with Z=21-30 and targets with half-lives exceeding 50 d.The influence of mass asymmetry and isotopic dependence on the projectile and target nuclei was investigated in detail.The reactions^(254)Es(^(46)Ti,3n)^(297)121 and^(252)Es(^(46)Ti,3n)^(295)121 were found to be experimentally feasible for synthesizing superheavy element Z=121,with maximal evaporation residue cross sections of 6.619 and 4.123 fb at 219.9 and 223.9 MeV,respectively.

Effects of Maillard reaction and its product AGEs on aging and age-related diseases

Maillard reaction(MR)is a non-enzymatic browning reaction commonly seen in food processing,which occurs between reducing sugars and compounds with amino groups.Despite certain advantages based on Maillard reaction products(MRPs)found in some food for health and storage application have appeared,however,the MR occurring in human physiological environment can produce advanced glycation end products(AGEs)by non-enzymatic modification of macromolecules such as proteins,lipids and nucleic acid,which could change the structure and functional activity of the molecules themselves.In this review,we take AGEs as our main object,on the one hand,discuss physiologic aging,that is,age-dependent covalent cross-linking and modification of proteins such as collagen that occur in eyes and skin containing connective tissue.On the other hand,pathological aging associated with autoimmune and inflammatory diseases,neurodegenerative diseases,diabetes and diabetic nephropathy,cardiovascular diseases and bone degenerative diseases have been mainly proposed.Based on the series of adverse effects of accelerated aging and disease pathologies caused by MRPs,the possible harm caused by some MR can be slowed down or inhibited by artificial drug intervention,dietary pattern and lifestyle control.It also stimulates people's curiosity to continue to explore the potential link between the MR and human aging and health,which should be paid more attention to for the development of life sciences.

Theoretical analysis of the double-differential cross-sections of neutron,proton,deuteron,^(3)He,andαfor the p+^(6) Li reaction

Based on the unified Hauser–Feshbach and exciton model,which can describe the particle emission processes between discrete energy levels with energy,angular momentum,and parity conservations,a statistical theory of light nucleus reaction(STLN)is developed to calculate the double-differential cross-sections of the outgoing neutron and light charged particles for the proton-induced^(6) Li reaction.A significant difference is observed between the p+^(6) Li and p+^(7) Li reactions owing to the discrepancies in the energy-level structures of the targets.The reaction channels,including sequential and simultaneous emission processes,are analyzed in detail.Taking the double-differential cross-sections of the outgoing proton as an example,the influence of contaminations(such as^(1) H,^(7)Li,^(12)C,and^(16)O)on the target is identified in terms of the kinetic energy of the first emitted particles.The optical potential parameters of the proton are obtained by fitting the elastic scattering differential cross-sections.The calculated total double-differential cross-sections of the outgoing proton and deuteron at E_(p)=14 MeV agree well with the experimental data for different outgoing angles.Simultaneously,the mixed double differential cross-sections of^(3) He andαare in good agreement with the measurements.The agreement between the measured data and calculated results indicates that the two-body and three-body breakup reactions need to be considered,and the pre-equilibrium reaction mechanism dominates the reaction processes.Based on the STLN model,a PLUNF code for the p+^(6) Li reaction is developed to obtain an ENDF-6-formatted file of the double-differential cross-sections of the nucleon and light composite charged particles.

Efficient removal of Al(Ⅲ)and P507 from high concentration MgCl_(2)solution based on in-situ reaction strategy

For a highly efficient recycling of a wastewater containing a high concentration of MgCl_2,Al(Ⅲ)and P507 were scheduled to be removed in advance.In this study,the in-situ removal of Al(Ⅲ)and P507 from a high concentration MgCl_(2)solution at different pH values and Al/P molar ratios was investigated.The results showed that P507 formed organic complexes of Al_x(OH)_y~(Z+)-P507 at pH of 2.0-4.0.At pH of 4.0-5.0,Al(Ⅲ)precipitated and transferred into Al(OH)_(3)with a flocculent amorphous morphology.Active sites on the Al(OH)_(3)surface enhanced the removal efficiency of P507.At pH of 6.0-6.5,Al(Ⅲ)and Mg(Ⅱ)formed layered crystalline Al(OH)_(3)and MgAl_2(OH)_(8with)small pore channels and fewer active sites,resulting in a reduced removal efficiency of P507.When the Al/P molar ratio exceeded 13 and the pH was between 4.0 and 5.0,the removal rates of both Al(Ⅲ)and P507 were higher than98%,while the concentration loss of Mg(Ⅱ)was only 0.2%-0.9%.

The reaction mechanism and interfacial crystallization of Al nanoparticle-embedded Ni under shock loading

The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

Influence of initial check, information exchange, final accuracy check, reaction information nursing on the psychology of elderly with lung cancer

BACKGROUND As one of the fatal diseases with high incidence,lung cancer has seriously endangered public health and safety.Elderly patients usually have poor self-care and are more likely to show a series of psychological problems.AIM To investigate the effectiveness of the initial check,information exchange,final accuracy check,reaction(IIFAR)information care model on the mental health status of elderly patients with lung cancer.METHODS This study is a single-centre study.We randomly recruited 60 elderly patients with lung cancer who attended our hospital from January 2021 to January 2022.These elderly patients with lung cancer were randomly divided into two groups,with the control group taking the conventional propaganda and education and the observation group taking the IIFAR information care model based on the conventional care protocol.The differences in psychological distress,anxiety and depression,life quality,fatigue,and the locus of control in psychology were compared between these two groups,and the causes of psychological distress were analyzed.RESULTS After the intervention,Distress Thermometer,Hospital Anxiety and Depression Scale(HADS)for anxiety and the HADS for depression,Revised Piper’s Fatigue Scale,and Chance Health Locus of Control scores were lower in the observation group compared to the pre-intervention period in the same group and were significantly lower in the observation group compared to those of the control group(P<0.05).After the intervention,Quality of Life Questionnaire Core 30(QLQ-C30),Internal Health Locus of Control,and Powerful Others Health Locus of Control scores were significantly higher in the observation and the control groups compared to the pre-intervention period in their same group,and QLQ-C30 scores were significantly higher in the observation group compared to those of the control group(P<0.05).CONCLUSION The IIFAR information care model can help elderly patients with lung cancer by reducing their anxiety and depression,psychological distress,and fatigue,improving their tendencies on the locus of control in psychology,and enhancing their life qualities.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.

Oxidation Evolution and Activity Origin of N-Doped Carbon in the Oxygen Reduction Reaction

N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.

Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.

Towards a new avenue for rapid synthesis of electrocatalytic electrodes via laser-induced hydrothermal reaction for water splitting

Electrochemical production of hydrogen from water requires the development ofelectrocatalysts that are active,stable,and low-cost for water splitting.To address these challenges,researchers are increasingly exploring binder-free electrocatalytic integratedelectrodes (IEs) as an alternative to conventional powder-based electrode preparation methods,for the former is highly desirable to improve the catalytic activity and long-term stability for large-scale applications of electrocatalysts.Herein,we demonstrate a laser-inducedhydrothermal reaction (LIHR) technique to grow NiMoO4nanosheets on nickel foam,which is then calcined under H2/Ar mixed gases to prepare the IE IE-NiMo-LR.This electrode exhibits superior hydrogen evolution reaction performance,requiring overpotentials of 59,116 and143 mV to achieve current densities of 100,500 and 1000 mA·cm-2.During the 350 h chronopotentiometry test at current densities of 100 and 500 m A·cm-2,the overpotentialremains essentially unchanged.In addition,NiFe-layered double hydroxide grown on Ni foam is also fabricated with the same LIHR method and coupled with IE-NiMo-IR to achieve water splitting.This combination exhibits excellent durability under industrial current density.The energy consumption and production efficiency of the LIHR method are systematicallycompared with the conventional hydrothermal method.The LIHR method significantly improves the production rate by over 19 times,while consuming only 27.78%of the total energy required by conventional hydrothermal methods to achieve the same production.

Direct measurement of the break-out ^(19)F(p,γ)^(20)Ne reaction in the China Jinping underground laboratory(CJPL)

Calcium production and the stellar evolution of first-generation stars remain fascinating mysteries in astrophysics.As one possible nucleosynthesis scenario,break-out from the hot carbon–nitrogen–oxygen(HCNO)cycle was thought to be the source of the calcium observed in these oldest stars.However,according to the stellar modeling,a nearly tenfold increase in the thermonuclear rate ratio of the break-out ^(19)F(p,γ)^(20) Ne reaction with respect to the competing ^(19)F(p,α)^(16) O back-processing reaction is required to reproduce the observed calcium abundance.We performed a direct measurement of this break-out reaction at the China Jinping underground laboratory.The measurement was performed down to the low-energy limit of E_(c.m.)=186 keV in the center-of-mass frame.The key resonance was observed at 225.2 keV for the first time.At a temperature of approximately 0.1 GK,this new resonance enhanced the thermonuclear ^(19)F(p,γ)^(20) Ne rate by up to a factor of≈7.4,compared with the previously recommended NACRE rate.This is of particular interest to the study of the evolution of the first stars and implies a stronger breakdown in their“warm”CNO cycle through the ^(19)F(p,γ)^(20) Ne reaction than previously envisioned.This break-out resulted in the production of the calcium observed in the oldest stars,enhancing our understanding of the evolution of the first stars.

Petrology of Spinel-Lherzolite Xenoliths from Mazéléand Others Northen Xenoliths Localities of Cameroon Volcanic Line: Exchange Reactions and Equilibrium State

The alkaline volcanism of the Cameroon Volcanic Line in its northern domain has raised many fresh enclaves of peridotites. The samples selected come from five (05) different localities (Liri, in the plateau of Kapsiki, Mazélé in the NE of Ngaoundéré, Tello and Ganguiré in the SE of Ngaoundéré and Likok, locality located in the west of Ngaoundé). The peridotite enclaves of the above localities show restricted mineralogical variation. Most are four-phase spinel-lherzolites, indicating that this is the main lithology that forms the lithospheric mantle below the shallow zone. No traces of garnet or primary plagioclase were detected, which strongly limits the depth range from which the rock fragments were sampled. The textures and the wide equilibrium temperatures (884˚C - 1115˚C) indicate also entrainment of lherzolite xenoliths from shallow depths within the lithosphere and the presence of mantle diapirism. The exchange reactions and equilibrium state established in this work make it possible to characterize the chemical composition of the upper mantle of each region and test the equilibrium state of the phases between them. Variations of major oxides and incompatible elemental concentrations in clinopyroxene indicate a primary control by partial melting. The absence of typical “metasomatic” minerals, low equilibration temperatures and enriched LREE patterns indicate that the upper mantle below septentrional crust of Cameroun underwent an event of cryptic metasomatic enrichment prior to partial melting. The distinctive chemical features, LREE enrichment, strong U, Ce and Pr, depletion relative to Ba, Nb, La, Pb, and T, fractionation of Zr and Hf and therefore ligh high Zr/Hf ratio, low La/Yb, Nb/La and Ti/Eu are all results of interaction of refractory peridotite residues with carbonatite melts.

The manipulation of rectifying contact of Co and nitrogen-doped carbon hierarchical superstructures toward high-performance oxygen reduction reaction

Rational design and construction of oxygen reduction reaction(ORR)electrocatalysts with high activity,good stability,and low price are essential for the practical applications of renewable energy conversion devices,such as metal-air batteries.Electronic modification through constructing metal/semiconductor Schottky heterointerface represents a powerful strategy to enhance the electrochemical performance.Herein,we demonstrate a concept of Schottky electrocatalyst composed of uniform Co nanoparticles in situ anchored on the carbon nanotubes aligned on the carbon nanosheets(denoted as Co@N-CNTs/NSs hereafter)toward ORR.Both experimental findings and theoretical simulation testify that the rectifying contact could impel the voluntary electron flow from Co to N-CNTs/NSs and create an internal electric field,thereby boosting the electron transfer rate and improving the intrinsic activity.As a consequence,the Co@N-CNTs/NSs deliver outstanding ORR activity,impressive long-term durability,excellent methanol tolerance,and good performance as the air-cathode in the Zn-air batteries.The design concept of Schottky contact may provide the innovational inspirations for the synthesis of advanced catalysts in sustainable energy conversion fields.

Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Pyrolysis of Copper Phthalocyanine as Non-noble Metal Electrocatalysts for Oxygen Reduction Reaction

We investigated the relationship between oxygen reduction reaction(ORR)activity and the pyrolysis temperature(650-850℃)of CuPc in alkaline solution.The highly active sites were formed through the decomposition of CuPc or Cu-N_(4) structure after releasing 4-nitrophthalonitrile.Cu-Nx incorporated with carbon were the main active sites.The XPS measurement results show that,at lower temperature,the contents of pyridinic-N and pyrrolic-N account for the most of the total N.As the temperature is higher than 750℃,the content of graphitic N(26.11%)increases and pyridinic-N(58.81%)becomes the dominant specie.When the temperature is higher than 850℃,the content of graphitic N increases remarkably and becomes the dominant species.Moreover,the specific surface areas decrease with increased pyrolysis temperature.Benefiting from the synergistic effect,the pyrolysis temperature at 750℃of CuPc displays superior electrocatalytic properties.The obtained results reveal that the fabricated non-noble metal catalysts can be used as low-cost,efficient catalyst for water splitting ORR in metal-air batteries and fuel cells.

Mapping out the reaction network of humin formation at the initial stage of fructose dehydration in water

The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water is delineated by combined experimental,spectroscopic,and theoretical studies.Three bimolecular reaction pathways to build up soluble humins are demonstrated.That is,the intermolecular etherification of β-furanose at room temperature initiates the C12 path,whereas the C-C cleavage of a-furanose at 130-150℃ leads to C11 path,and that of open-chain fructose at 180℃ to C11' path.The successive intramolecular dehydrations and condensations of the as-formed bimolecular intermediates lead to three types of soluble humins.We show that the C12 path could be restrained by using HCl or AlCl_(3) catalyst,and both the C12 and C110 paths could be effectively inhibited by adding THF as a co-solvent or accelerating heating rate via microwave heating.