Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the tw...Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the two components.We carried out first‐principles calculations at the PBE+U level to investigate the Pd‐doping effect on CH4reactivity over the Co3O4catalyst.Because of the structural complexity of the Pd‐doped Co3O4catalyst,we built Pd‐doped catalyst models using Co3O4(001)slabs with two different terminations and examined CH4reactivity over the possible Pd?O active sites.A low energy barrier of0.68eV was predicted for CH4dissociation over the more reactive Pd‐doped Co3O4(001)surface,which was much lower than the0.98and0.89eV that was predicted previously over the more reactive pure Co3O4(001)and(011)surfaces,respectively.Using a simple model,we predicted CH4reaction rates over the pure Co3O4(001)and(011)surfaces,and Co3O4(001)surfaces with different amounts of Pd dopant.Our theoretical results agree well with the available experimental data,which suggests a strong synergy between the Pd dopant and the Co3O4catalyst,and leads to a significant increase in CH4reaction rate.展开更多
The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fab...The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fabricated using transition‐metal(TM)atoms(TM=Sc−Zn)doped into g‐CN monolayers.The electrochemical mechanism of APCs for an NRR has been reported by well‐defined density functional theory calculations.The calculated limiting potentials were−0.47 and−0.78 V for the Fe_(2)@CN and Co_(2)@CN catalysts,respectively.Owing to its high suppression of hydrogen evolution reactions,Co_(2)@CN is a superior electrocatalytic material for a N_(2)fixation.Stable Fe_(2)@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity.The two‐way charge transfer affirmed the donation‐acceptance procedure between N_(2)and Fe_(2)@CN or Co_(2)@CN,which play a crucial role in the activation of inert N≡N bonds.This study provides an in‐depth investigation into atom‐pair catalysts and will open up new avenues for highly efficient g‐CN‐based nanostructures for an NRR.展开更多
This paper studies supersonic jet-cooled 1-fluoronaphthalene （1FN） clusters by ultraviolet （UV） laser ionization at 281 nm in a time-of-flight mass spectrometer. The （1FN）＋ （n=1-3） series cluster ions are obs...This paper studies supersonic jet-cooled 1-fluoronaphthalene （1FN） clusters by ultraviolet （UV） laser ionization at 281 nm in a time-of-flight mass spectrometer. The （1FN）＋ （n=1-3） series cluster ions are observed where the signal intensity decreases with increasing cluster size. The effects of sample inlet pressures and ionization laser fluxes to mass spectral distribution are measured. Using density functional theory calculations, it obtains a planar geometric structure of 1FN dimer which is combined through two hydrogen bonds. The mass spectra indicate that the intensity of 1FN trimer is much weaker than that of 1FN dimer and this feature is attributed to the fact that the dimer may form the first ＂shell＂ in geometric structure while the larger clusters are generated based on this fundamental unit.展开更多
Arsenic can diffuse into high-κ dielectrics during OaAs-based metal oxide semiconductor transistor process, which causes the degradation of gate dielectrics. To explore the origins of the degradation, we employ nonlo...Arsenic can diffuse into high-κ dielectrics during OaAs-based metal oxide semiconductor transistor process, which causes the degradation of gate dielectrics. To explore the origins of the degradation, we employ nonlocal B3LYP hybrid functional to study arsenic related defects in ZrO2. Via band alignments between the OaAs and ZrO2, we are able to determine the defect formation energy in the GaAs relative to the ZrO2 band gap and assess how they will affect the device performance. Arsenic at the interstitial site serves as a source of positive fixed charge while at the oxygen or zirconium substitutional site changes its charge state within the band gap of GaAs. Moreover, it is found that arsenic related defects produce conduction band offset reduction and gap states, which will increase the gate leakage current.展开更多
In this paper, we perform the density functional theory （DFT） -based calculations by the first-principles pseudopo- tential method to investigate the physical properties of the newly discovered superconductor LaRu2A...In this paper, we perform the density functional theory （DFT） -based calculations by the first-principles pseudopo- tential method to investigate the physical properties of the newly discovered superconductor LaRu2As2 for the first time. The optimized structural parameters are in good agreement with the experimental results. The calculated independent elas- tic constants ensure the mechanical stability of the compound. The calculated Cauchy pressure, Pugh＇s ratio as well as Poisson＇s ratio indicate that LaRu2As2 should behave as a ductile material. Due to low Debye temperature, LaRu2As2 may be used as a thermal barrier coating （TBC） material. The new compound should exhibit metallic nature as its valence bands overlap considerably with the conduction bands. LaRu2As2 is expected to be a soft material and easily machinable because of its low hardness value of 6.8 GPa. The multi-band nature is observed in the calculated Fermi surface. A highly anisotropic combination of ionic, covalent and metallic interactions is expected to be in accordance with charge density calculation.展开更多
The role of additional ternary alloying elements on the performance of stationary TiFe-based hydrogen storage alloys was investigated based on first-principles density functional theory calculations.As a basic step fo...The role of additional ternary alloying elements on the performance of stationary TiFe-based hydrogen storage alloys was investigated based on first-principles density functional theory calculations.As a basic step for examinations,the site preference of each alloying element in the stoichiometric and nonstoichiometric B2TiFe compounds was clarified considering possible antisite defects.Based on the revealed site preference,the effect of various possible ternary elements on the hydrogen storage was examined by focusing on the formation enthalpies of TiFeH and TiFeH_(2) hydrides,which were closely related to the change in the location of plateaus in the pressure-composition-temperature curve.Several physical properties such as the volume expansion due to hydride formation were also examined to provide additional criteria for selecting optimum alloying conditions in future alloying design processes.Candidate alloying elements that maximize the grain boundary embrittlement due to the solute segregation were proposed for the enhanced initial activation of TiFe-based hydrogen storage alloys.展开更多
First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated resu...First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated results show that the structure and electronic properties of sulfide minerals surfaces have been influenced in presence of H2 O molecule. The adsorption of the flotation reagent at the interface of mineral-water would be different from that of mineral surface due to the changes of surface structures and electronic properties caused by H2 O molecule. Hence, the influence of H2 O molecule on the reaction of flotation reagent with sulfide mineral surface will attract more attention.展开更多
Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach...Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach to optimize its performance.However,there is a lack of systematic theoretical studies to reveal the quantitative relationships at the electronic level.Here,we develop a multi-level screening methodology to search for highly stable and active dopants for CoP catalysts.The density functional theory(DFT)calculations and symbolic regression(SR)were performed to investigate the relationship between the adsorption free energy(ΔG_(H^(*)))and 10 electronic parameters.The mathematic formulas derived from SR indicate that the difference of work function(ΔΦ)between doped metal and the acceptor plays the most important role in regulatingΔG_(H^(*)),followed by the d-band center(d-BC)of doped system.The descriptor of HER can be expressed asΔG_(H^(*))=1.59×√|0.188ΔΦ+d BC+0.120|1/2-0.166 with a high determination coefficient(R^(2)=0.807).Consistent with the theoretical prediction,experimental results show that the Al-CoP delivers superior electrocatalytic HER activity with a low overpotential of75 m V to drive a current density of 10 mA cm^(-2),while the overpotentials for undoped CoP,Mo-CoP,and V-CoP are 206,134,and 83 m V,respectively.The current work proves that theΔΦis the most significant regulatory parameter ofΔG_(H^(*))for ion-doped electrocatalysts.This finding can drive the discovery of high-performance ion-doped electrocatalysts,which is crucial for electrocatalytic water splitting.展开更多
The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single cry...The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single crystals grown on the surface of KTaO_(3) can accomplish photocatalytic overall water splitting for the first time.In order to comprehend the underlying mechanism of this photocatalytic system,we have performed a systematic study based on density functional theory first-principles calculations.Ta_(3)N_(5)(010)/KTaO_(3)(110)slab models have been built according to experimental observations by considering two common terminations of KTaO_(3)(110)surface,named as Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO.The formations of interfacial bonds are thermodynamically stable,showing a covalent interaction between two components of a heterostructure.Ta_(3)N_(5)/O_(2) has a higher mobility of photogenerated charge carriers and lower recombination rate of charge carriers than Ta_(3)N_(5)/KTaO.The light absorption of heterostructures displays the feature of KTaO_(3) in the short wavelength region and the characteristic of Ta_(3)N_(5) in the long wavelength region.The calculated band offsets show that Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO have distinct Type-II band alignments,with Ta_(3)N_(5) as the accumulator of photoinduced electrons in the former and the collector of photogenerated holes in the latter,respectively.The difference in charge density and electrostatic potential between two components acts as a driving force to promote the transfer of electrons and holes to different domains of the interface,which is beneficial to extend the lifetime of photoinduced carriers.Our results demonstrate that the function of Ta_(3)N_(5) in Ta_(3)N_(5)/KTaO_(3) photocatalytic system is determined by the termination property of KTaO_(3)(110)surface,which provides a likely reason of the observed photocatalytic activity of overall water splitting achieved by Ta_(3)N_(5) synthesized by using KTaO_(3) as a precursor for the nitridation reaction.展开更多
The thermodynamic stability and lithiated/delithiated potentials of LiFexMn1-xPO4 were studied with density functional theorical calculations. The results show that the formation free energy of the LiFexMn1-xPO4 solid...The thermodynamic stability and lithiated/delithiated potentials of LiFexMn1-xPO4 were studied with density functional theorical calculations. The results show that the formation free energy of the LiFexMn1-xPO4 solid solution is slightly higher than that of the phase-separated mixture of LiFePO4 and LiMnPO4, and the two forms may co-exist in the actual LiFexMn1-xPO4 materials. The calculation manifests that the lithiated/delithiated potentials of LiFexMn1-xPO4 solid solutions vary via the Mn/Fe ratio and the spatial arrangements of the transition metal ions, and the result is used to explain the shape of capacity-voltage curves. Experimentally, we have synthesized the LiFexMn1-xPO4 materials by solid-phase reaction method. The existence of the LiFexMn1-xPO4 solid solution is thought to be responsible for the appearance of additional capacity-voltage plateau observed in the experiment.展开更多
P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,pero...P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,perovskite single crystal(C_(4)H_(9)NH_(3))_(2)PbI_(4)has been successfully synthesized via solution method.The obtained product was analyzed by single crystal X-ray diffraction.With the space group Pbca,orthorhombic(C_(4)H_(9)NH_(3))_(2)PbI_(4)layered perovskite structure consists of an extended two-dimensional network of corner-sharing PbI_(6)octahedron.Single layer perovskite sheets of distorted PbI_(6)octahedron alternated with protonated n-butylammonium cation bilayers,which offers many advantages and provides the possibility of forming a gas sensor device based on the change of resistances.Density functional theory(DFT)simulations regarding the adsorption energy revealed that this organicinorganic hybrid perovskite compound has excellent selectivity toward p-xylene compared with other gases including C_(2)H_(5)OH,C_(6)H_(6),CH_(2)Cl_(2),HCHO,CH_(3)COCH_(3)and C_(7)H_(8).The calculation of electron density,density of states and electron density difference showed the sensing mechanism of p-C_(8)H_(10)is mainly derived from physical adsorption-desorption in view of electron transfer.展开更多
A supramolecular 1D ferromagnetic system was studied experimentally as well as theoretically.Hybrid density functional theory（DFT） calculations were based on the X-ray analysis.The results of DFT calculations and Mc...A supramolecular 1D ferromagnetic system was studied experimentally as well as theoretically.Hybrid density functional theory（DFT） calculations were based on the X-ray analysis.The results of DFT calculations and McConnell mechanism have contributed to the understanding of the factors governing the exchange coupling of magnetism in the crystal packing.Both the experimental evidence and theoretical calculation indicate that spin density in 2-iodo nitronyl nitroxide（INN） radicals confirms 1D ferromagnetic chain with inter-chain antiferromagnetic interaction.展开更多
We used density functional theory(DFT)calculations to study the influence of alkali earth metal element(AE)doping on the crystal structure and electronic band structure ofα-Si3N4.The diversity of atomic radii of alka...We used density functional theory(DFT)calculations to study the influence of alkali earth metal element(AE)doping on the crystal structure and electronic band structure ofα-Si3N4.The diversity of atomic radii of alkaline earth metal elements results in structural expansion when they were doped into theα-Si3N4 lattice.Formation energies of the doped structures indicate that dopants prefer to occupy the interstitial site under the nitrogen-deficient environment,while substitute Si under the nitrogen-rich environment,which provides a guide to synthesizingα-Si3N4 with different doping types by controlling nitrogen conditions.For electronic structures,energy levels of the dopants appear in the bottom of the conduction band or the top of the valence band or the forbidden band,which reduces the bandgap ofα-Si3N4.展开更多
The plane wave pseudo-potential method was used to investigate the structural, electronic, and elastic properties of Cd Se_（1-x）Te_x in the zinc blende phase. It is observed that the electronic properties are improv...The plane wave pseudo-potential method was used to investigate the structural, electronic, and elastic properties of Cd Se_（1-x）Te_x in the zinc blende phase. It is observed that the electronic properties are improved considerably by using LDA ＋ U as compared to the LDA approach. The calculated lattice constants and bulk moduli are also comparable to the experimental results. The cohesive energies for pure Cd Se and Cd Te binary and their mixed alloys are calculated. The second-order elastic constants are also calculated by the Lagrangian theory of elasticity. The elastic properties show that the studied material has a ductile nature.展开更多
The effects of seemingly inert alkali metal(AM)cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts ...The effects of seemingly inert alkali metal(AM)cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts in recent years.The hydrogen and oxygen evolution reactions during alkaline water electrolysis and the oxygen electro-reduction taking place in fuel cells are of particular importance.There is no universal theory explaining all the details of the AM cation effect in electrocatalysis.For example,it remains unclear how“spectator”AM-cations can change the kinetics of electrocatalytic reactions often more significantly than the modifications of the elec-trode structure and composition.This situation originates partly from a lack of systematic experimental and theoretical studies of this phenomenon.The present work exploits impedance spectroscopy to investigate the influence of the AM cations on the mechanism of the hydrogen evolution reaction at Pt microelectrodes.The activity follows the trend:Li^(+)≥Na^(+)≥K^(+)≥Cs^(+),where the highest activity corresponds to 0.1 M LiOH electrolytes at low overpotentials.We demonstrate that the nature of the AM cations also changes the relative contribution of the Volmer–Heyrovsky and Volmer–Tafel mechanisms to the overall reaction,with the former being more important for LiOH electrolytes.Our density functional theory-based thermodynamics and molecular dynamics calculations support these findings.展开更多
Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structu...Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.展开更多
In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due t...In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due to the rich host-vip recognition in their rigid electron-rich cavities.However,most reported pillararenes are functionalized by alkoxy modification,which results in poor charge transfer nature and weak fluorescence response.A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine(Ar_(3)N)and electron-deficient triarylborane(Ar_(3)B)into pillar[5]arene skeleton,which significantly improved its luminescence behavior and was further used for fluorescence detection applications.The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size.It was found that P5BN,as a fluorescent sensor,showed a highly sensitive and selective response to L-arginine(L-Arg),resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^(-8) mol/L.The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.展开更多
Hyperforatone A(1),the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol,possessed an unusual bicyclo[5.4.0]undecane skeleton bearing a 5/7/6/5 ring system,and two known biosynthetically related precurs...Hyperforatone A(1),the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol,possessed an unusual bicyclo[5.4.0]undecane skeleton bearing a 5/7/6/5 ring system,and two known biosynthetically related precursors(2 and 3)were isolated from Hypericum perforatum(St.John's wort).The structure and absolute configuration were unambiguously confirmed by a combination of comprehensive spectroscopic data,computational methods including residual dipolar couplings(RDCs),and X-ray crystallography.Density functional theory(DFT)calculations revealed that the cationic cyclization reaction was key to proposed formation mechanism for hyperforatone A.Furthermore,in vitro and in vivo experiments demonstrated that compound 1 was a potential anti-neuroinfiammatory agent.展开更多
Lithium-sulfur batteries(LSBs)are considered as the promising solution to replace conventional lithium-ion batteries due to satisfactory energy density.In recent times,the LSBs field has been found to face some diffic...Lithium-sulfur batteries(LSBs)are considered as the promising solution to replace conventional lithium-ion batteries due to satisfactory energy density.In recent times,the LSBs field has been found to face some difficulties in exploring practical applications in which cycling stability and cycle life are awful owing to the shuttling effect of lithium polysulfides(LiPSs)and low sulfur utilization.In this work,by synthesizing Co_(3)Se_(4) nanoparticles onto N-doped carbon(NC)polyhedra interconnected with carbon nanotubes(CNTs),NC@Co_(3)Se_(4)/CNTs is proposed as a multifunctional sulfur carrier.The Co_(3)Se_(4) nanoparticles fleetly catalyze the conversion of LiPSs and availably immobilize LiPSs.Meanwhile,the NC polyhedral skeleton enhances the electronic conductivity of active sulfur,while the CNTs facilitate Li+diffusion and supply a mass of conductive channels.Density-functional theory(DFT)calculations demonstrate the relevant mechanisms.That is to say,the NC@Co_(3)Se_(4)/CNTs benefit from the synergistic effect of Co_(3)Se_(4) nanoparticles(highly catalytic ability and strong adsorbability for LiPSs)and the special carbonaceous structure,rapidly converting LiPSs and inhibiting the shuttle of LiPSs.Therefore,lithium-sulfur battery assembled with S/NC@Co_(3)Se_(4)/CNTs cathode as well as nitrogen and sulfur co-doped carbon-coated polypropylene(N,S-C/PP)separator possesses a high initial discharge capacity of 1413 mAh·g-1 at 0.12C and persistently circulates for 1000 cycles at 1C with a capacity attenuation rate per cycle of 0.034%.This work provides a realistic idea for the use of transition metal selenide in the field of high-performance LSBs.展开更多
Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly ...Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.展开更多
基金supported by the National Natural Science Foundation of China(21473233,21403277)the Energy Technologies Institute LLP,UK~~
文摘Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the two components.We carried out first‐principles calculations at the PBE+U level to investigate the Pd‐doping effect on CH4reactivity over the Co3O4catalyst.Because of the structural complexity of the Pd‐doped Co3O4catalyst,we built Pd‐doped catalyst models using Co3O4(001)slabs with two different terminations and examined CH4reactivity over the possible Pd?O active sites.A low energy barrier of0.68eV was predicted for CH4dissociation over the more reactive Pd‐doped Co3O4(001)surface,which was much lower than the0.98and0.89eV that was predicted previously over the more reactive pure Co3O4(001)and(011)surfaces,respectively.Using a simple model,we predicted CH4reaction rates over the pure Co3O4(001)and(011)surfaces,and Co3O4(001)surfaces with different amounts of Pd dopant.Our theoretical results agree well with the available experimental data,which suggests a strong synergy between the Pd dopant and the Co3O4catalyst,and leads to a significant increase in CH4reaction rate.
文摘The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fabricated using transition‐metal(TM)atoms(TM=Sc−Zn)doped into g‐CN monolayers.The electrochemical mechanism of APCs for an NRR has been reported by well‐defined density functional theory calculations.The calculated limiting potentials were−0.47 and−0.78 V for the Fe_(2)@CN and Co_(2)@CN catalysts,respectively.Owing to its high suppression of hydrogen evolution reactions,Co_(2)@CN is a superior electrocatalytic material for a N_(2)fixation.Stable Fe_(2)@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity.The two‐way charge transfer affirmed the donation‐acceptance procedure between N_(2)and Fe_(2)@CN or Co_(2)@CN,which play a crucial role in the activation of inert N≡N bonds.This study provides an in‐depth investigation into atom‐pair catalysts and will open up new avenues for highly efficient g‐CN‐based nanostructures for an NRR.
文摘This paper studies supersonic jet-cooled 1-fluoronaphthalene （1FN） clusters by ultraviolet （UV） laser ionization at 281 nm in a time-of-flight mass spectrometer. The （1FN）＋ （n=1-3） series cluster ions are observed where the signal intensity decreases with increasing cluster size. The effects of sample inlet pressures and ionization laser fluxes to mass spectral distribution are measured. Using density functional theory calculations, it obtains a planar geometric structure of 1FN dimer which is combined through two hydrogen bonds. The mass spectra indicate that the intensity of 1FN trimer is much weaker than that of 1FN dimer and this feature is attributed to the fact that the dimer may form the first ＂shell＂ in geometric structure while the larger clusters are generated based on this fundamental unit.
基金Supported by the Key Project of Education Department of China under Grant No 211035the Science Foundation from Education Department of Liaoning Province under Grant No L2014445
文摘Arsenic can diffuse into high-κ dielectrics during OaAs-based metal oxide semiconductor transistor process, which causes the degradation of gate dielectrics. To explore the origins of the degradation, we employ nonlocal B3LYP hybrid functional to study arsenic related defects in ZrO2. Via band alignments between the OaAs and ZrO2, we are able to determine the defect formation energy in the GaAs relative to the ZrO2 band gap and assess how they will affect the device performance. Arsenic at the interstitial site serves as a source of positive fixed charge while at the oxygen or zirconium substitutional site changes its charge state within the band gap of GaAs. Moreover, it is found that arsenic related defects produce conduction band offset reduction and gap states, which will increase the gate leakage current.
文摘In this paper, we perform the density functional theory （DFT） -based calculations by the first-principles pseudopo- tential method to investigate the physical properties of the newly discovered superconductor LaRu2As2 for the first time. The optimized structural parameters are in good agreement with the experimental results. The calculated independent elas- tic constants ensure the mechanical stability of the compound. The calculated Cauchy pressure, Pugh＇s ratio as well as Poisson＇s ratio indicate that LaRu2As2 should behave as a ductile material. Due to low Debye temperature, LaRu2As2 may be used as a thermal barrier coating （TBC） material. The new compound should exhibit metallic nature as its valence bands overlap considerably with the conduction bands. LaRu2As2 is expected to be a soft material and easily machinable because of its low hardness value of 6.8 GPa. The multi-band nature is observed in the calculated Fermi surface. A highly anisotropic combination of ionic, covalent and metallic interactions is expected to be in accordance with charge density calculation.
基金supported by the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(Nos.NRF-2019M3E6A1103984 and NRF-2019M3D1A1079214)。
文摘The role of additional ternary alloying elements on the performance of stationary TiFe-based hydrogen storage alloys was investigated based on first-principles density functional theory calculations.As a basic step for examinations,the site preference of each alloying element in the stoichiometric and nonstoichiometric B2TiFe compounds was clarified considering possible antisite defects.Based on the revealed site preference,the effect of various possible ternary elements on the hydrogen storage was examined by focusing on the formation enthalpies of TiFeH and TiFeH_(2) hydrides,which were closely related to the change in the location of plateaus in the pressure-composition-temperature curve.Several physical properties such as the volume expansion due to hydride formation were also examined to provide additional criteria for selecting optimum alloying conditions in future alloying design processes.Candidate alloying elements that maximize the grain boundary embrittlement due to the solute segregation were proposed for the enhanced initial activation of TiFe-based hydrogen storage alloys.
基金Project(51164001)supported by the National Natural Science Foundation of China
文摘First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated results show that the structure and electronic properties of sulfide minerals surfaces have been influenced in presence of H2 O molecule. The adsorption of the flotation reagent at the interface of mineral-water would be different from that of mineral surface due to the changes of surface structures and electronic properties caused by H2 O molecule. Hence, the influence of H2 O molecule on the reaction of flotation reagent with sulfide mineral surface will attract more attention.
基金Financial support from the National Natural Science Foundation of China(21676216)the Special project of Shaanxi Provincial Education Department(20JC034)+1 种基金GHfund B(202202022563)Hefei Advanced Computing Center。
文摘Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach to optimize its performance.However,there is a lack of systematic theoretical studies to reveal the quantitative relationships at the electronic level.Here,we develop a multi-level screening methodology to search for highly stable and active dopants for CoP catalysts.The density functional theory(DFT)calculations and symbolic regression(SR)were performed to investigate the relationship between the adsorption free energy(ΔG_(H^(*)))and 10 electronic parameters.The mathematic formulas derived from SR indicate that the difference of work function(ΔΦ)between doped metal and the acceptor plays the most important role in regulatingΔG_(H^(*)),followed by the d-band center(d-BC)of doped system.The descriptor of HER can be expressed asΔG_(H^(*))=1.59×√|0.188ΔΦ+d BC+0.120|1/2-0.166 with a high determination coefficient(R^(2)=0.807).Consistent with the theoretical prediction,experimental results show that the Al-CoP delivers superior electrocatalytic HER activity with a low overpotential of75 m V to drive a current density of 10 mA cm^(-2),while the overpotentials for undoped CoP,Mo-CoP,and V-CoP are 206,134,and 83 m V,respectively.The current work proves that theΔΦis the most significant regulatory parameter ofΔG_(H^(*))for ion-doped electrocatalysts.This finding can drive the discovery of high-performance ion-doped electrocatalysts,which is crucial for electrocatalytic water splitting.
基金financially supported by the Natural Science Foundation of Liaoning Province(Grant No.2019-ZD-0304)the Educational Department of Liaoning Province(Grant No.LJ2019009)+1 种基金Liaoning BaiQianWan Talents Program,Doctoral Start-up Foundation of Liaoning Province(Grant No.20170520231)the open fund of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics(Grant No.SKLMRDK202001),Chinese Academy of Sciences。
文摘The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single crystals grown on the surface of KTaO_(3) can accomplish photocatalytic overall water splitting for the first time.In order to comprehend the underlying mechanism of this photocatalytic system,we have performed a systematic study based on density functional theory first-principles calculations.Ta_(3)N_(5)(010)/KTaO_(3)(110)slab models have been built according to experimental observations by considering two common terminations of KTaO_(3)(110)surface,named as Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO.The formations of interfacial bonds are thermodynamically stable,showing a covalent interaction between two components of a heterostructure.Ta_(3)N_(5)/O_(2) has a higher mobility of photogenerated charge carriers and lower recombination rate of charge carriers than Ta_(3)N_(5)/KTaO.The light absorption of heterostructures displays the feature of KTaO_(3) in the short wavelength region and the characteristic of Ta_(3)N_(5) in the long wavelength region.The calculated band offsets show that Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO have distinct Type-II band alignments,with Ta_(3)N_(5) as the accumulator of photoinduced electrons in the former and the collector of photogenerated holes in the latter,respectively.The difference in charge density and electrostatic potential between two components acts as a driving force to promote the transfer of electrons and holes to different domains of the interface,which is beneficial to extend the lifetime of photoinduced carriers.Our results demonstrate that the function of Ta_(3)N_(5) in Ta_(3)N_(5)/KTaO_(3) photocatalytic system is determined by the termination property of KTaO_(3)(110)surface,which provides a likely reason of the observed photocatalytic activity of overall water splitting achieved by Ta_(3)N_(5) synthesized by using KTaO_(3) as a precursor for the nitridation reaction.
基金supported by the Science and Technology Foundation of Jiangsu Province(BK20151237)the Special Nano-technology of Suzhou(ZXG2013004)+2 种基金USTC-NSRL Association Fundingthe Collaborative Innovation Centre of Suzhou Nano Science and Technologythe Supercomputation Center of USTC
文摘The thermodynamic stability and lithiated/delithiated potentials of LiFexMn1-xPO4 were studied with density functional theorical calculations. The results show that the formation free energy of the LiFexMn1-xPO4 solid solution is slightly higher than that of the phase-separated mixture of LiFePO4 and LiMnPO4, and the two forms may co-exist in the actual LiFexMn1-xPO4 materials. The calculation manifests that the lithiated/delithiated potentials of LiFexMn1-xPO4 solid solutions vary via the Mn/Fe ratio and the spatial arrangements of the transition metal ions, and the result is used to explain the shape of capacity-voltage curves. Experimentally, we have synthesized the LiFexMn1-xPO4 materials by solid-phase reaction method. The existence of the LiFexMn1-xPO4 solid solution is thought to be responsible for the appearance of additional capacity-voltage plateau observed in the experiment.
基金financially supported by the Natural Science Foundation of Hebei(Nos.F2020202027 and F2020202067)the Major National Science and Technology Special Projects(No.2016ZX02301003-004-007)+1 种基金the National Natural Science Foundation of China(No.21271139)the Natural Science Foundation of Tianjin(No.17JCTPJC54500)。
文摘P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,perovskite single crystal(C_(4)H_(9)NH_(3))_(2)PbI_(4)has been successfully synthesized via solution method.The obtained product was analyzed by single crystal X-ray diffraction.With the space group Pbca,orthorhombic(C_(4)H_(9)NH_(3))_(2)PbI_(4)layered perovskite structure consists of an extended two-dimensional network of corner-sharing PbI_(6)octahedron.Single layer perovskite sheets of distorted PbI_(6)octahedron alternated with protonated n-butylammonium cation bilayers,which offers many advantages and provides the possibility of forming a gas sensor device based on the change of resistances.Density functional theory(DFT)simulations regarding the adsorption energy revealed that this organicinorganic hybrid perovskite compound has excellent selectivity toward p-xylene compared with other gases including C_(2)H_(5)OH,C_(6)H_(6),CH_(2)Cl_(2),HCHO,CH_(3)COCH_(3)and C_(7)H_(8).The calculation of electron density,density of states and electron density difference showed the sensing mechanism of p-C_(8)H_(10)is mainly derived from physical adsorption-desorption in view of electron transfer.
基金Supported by the National Natural Science Foundation of China(No.21061009)
文摘A supramolecular 1D ferromagnetic system was studied experimentally as well as theoretically.Hybrid density functional theory（DFT） calculations were based on the X-ray analysis.The results of DFT calculations and McConnell mechanism have contributed to the understanding of the factors governing the exchange coupling of magnetism in the crystal packing.Both the experimental evidence and theoretical calculation indicate that spin density in 2-iodo nitronyl nitroxide（INN） radicals confirms 1D ferromagnetic chain with inter-chain antiferromagnetic interaction.
基金Funded by National Key Research and Development Program of China(No.2017YFB0310400)the National Natural Science Foundation of China(Nos.51872217,51932006,51972246 and 51521001)+3 种基金Fundamental Research Funds for the Central Universities in ChinaState Key Laboratory of Advanced Electromagnetic Engineering and Technology(Huazhong University of Science and Technology),the Joint Fund(No.6141A02022255)the Major Program of the Specialized Technological Innovation of HuBei Province,China(No.2019AFA176)the“111”Project(No.B13035)。
文摘We used density functional theory(DFT)calculations to study the influence of alkali earth metal element(AE)doping on the crystal structure and electronic band structure ofα-Si3N4.The diversity of atomic radii of alkaline earth metal elements results in structural expansion when they were doped into theα-Si3N4 lattice.Formation energies of the doped structures indicate that dopants prefer to occupy the interstitial site under the nitrogen-deficient environment,while substitute Si under the nitrogen-rich environment,which provides a guide to synthesizingα-Si3N4 with different doping types by controlling nitrogen conditions.For electronic structures,energy levels of the dopants appear in the bottom of the conduction band or the top of the valence band or the forbidden band,which reduces the bandgap ofα-Si3N4.
文摘The plane wave pseudo-potential method was used to investigate the structural, electronic, and elastic properties of Cd Se_（1-x）Te_x in the zinc blende phase. It is observed that the electronic properties are improved considerably by using LDA ＋ U as compared to the LDA approach. The calculated lattice constants and bulk moduli are also comparable to the experimental results. The cohesive energies for pure Cd Se and Cd Te binary and their mixed alloys are calculated. The second-order elastic constants are also calculated by the Lagrangian theory of elasticity. The elastic properties show that the studied material has a ductile nature.
基金the German Research Foundation (DFG) under Germany's excellence strategy–EXC 2089/1–390776260, Germany's excellence cluster “e-conversion”the DFG project BA 5795/6-1+2 种基金funding from the European Union's Horizon 2020 research and innovation program under grant agreement HERMES No 952184the National Science Foundation (NSF) support through the NSF CAREER award (Grant No. CBET1941204)financial support from TUM Innovation Network for Artificial Intelligence powered Multifunctional Material Design (ARTEMIS).
文摘The effects of seemingly inert alkali metal(AM)cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts in recent years.The hydrogen and oxygen evolution reactions during alkaline water electrolysis and the oxygen electro-reduction taking place in fuel cells are of particular importance.There is no universal theory explaining all the details of the AM cation effect in electrocatalysis.For example,it remains unclear how“spectator”AM-cations can change the kinetics of electrocatalytic reactions often more significantly than the modifications of the elec-trode structure and composition.This situation originates partly from a lack of systematic experimental and theoretical studies of this phenomenon.The present work exploits impedance spectroscopy to investigate the influence of the AM cations on the mechanism of the hydrogen evolution reaction at Pt microelectrodes.The activity follows the trend:Li^(+)≥Na^(+)≥K^(+)≥Cs^(+),where the highest activity corresponds to 0.1 M LiOH electrolytes at low overpotentials.We demonstrate that the nature of the AM cations also changes the relative contribution of the Volmer–Heyrovsky and Volmer–Tafel mechanisms to the overall reaction,with the former being more important for LiOH electrolytes.Our density functional theory-based thermodynamics and molecular dynamics calculations support these findings.
基金supported the Natural Science Foundation of Guangdong Province(Nos.2022A1515140085,2022A1515111022 and 2022A1515110275)the Major and Special Project in the Field of Intelligent Manufacturing of the Universities in Guangdong Province(No.2020ZDZX2067)+2 种基金the Natural Science Foundation of Huizhou University(No.HZU202004)the Professorial and Doctoral Scientific Research Foundation of Huizhou University(No.2020JB046)the Open Project Program of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices,Huizhou University(No.EFMDN2021004M).
文摘Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.
文摘In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due to the rich host-vip recognition in their rigid electron-rich cavities.However,most reported pillararenes are functionalized by alkoxy modification,which results in poor charge transfer nature and weak fluorescence response.A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine(Ar_(3)N)and electron-deficient triarylborane(Ar_(3)B)into pillar[5]arene skeleton,which significantly improved its luminescence behavior and was further used for fluorescence detection applications.The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size.It was found that P5BN,as a fluorescent sensor,showed a highly sensitive and selective response to L-arginine(L-Arg),resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^(-8) mol/L.The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.
基金financially supported by the National Natural Science Foundation of China(Nos.22077102,32201249)the Science and Technology Program of Gansu Province(No.22YF7GA046)。
文摘Hyperforatone A(1),the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol,possessed an unusual bicyclo[5.4.0]undecane skeleton bearing a 5/7/6/5 ring system,and two known biosynthetically related precursors(2 and 3)were isolated from Hypericum perforatum(St.John's wort).The structure and absolute configuration were unambiguously confirmed by a combination of comprehensive spectroscopic data,computational methods including residual dipolar couplings(RDCs),and X-ray crystallography.Density functional theory(DFT)calculations revealed that the cationic cyclization reaction was key to proposed formation mechanism for hyperforatone A.Furthermore,in vitro and in vivo experiments demonstrated that compound 1 was a potential anti-neuroinfiammatory agent.
基金supported by the National Natural Science Foundation of China(Nos.52130101 and 52271217)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH,20220201114GX).
文摘Lithium-sulfur batteries(LSBs)are considered as the promising solution to replace conventional lithium-ion batteries due to satisfactory energy density.In recent times,the LSBs field has been found to face some difficulties in exploring practical applications in which cycling stability and cycle life are awful owing to the shuttling effect of lithium polysulfides(LiPSs)and low sulfur utilization.In this work,by synthesizing Co_(3)Se_(4) nanoparticles onto N-doped carbon(NC)polyhedra interconnected with carbon nanotubes(CNTs),NC@Co_(3)Se_(4)/CNTs is proposed as a multifunctional sulfur carrier.The Co_(3)Se_(4) nanoparticles fleetly catalyze the conversion of LiPSs and availably immobilize LiPSs.Meanwhile,the NC polyhedral skeleton enhances the electronic conductivity of active sulfur,while the CNTs facilitate Li+diffusion and supply a mass of conductive channels.Density-functional theory(DFT)calculations demonstrate the relevant mechanisms.That is to say,the NC@Co_(3)Se_(4)/CNTs benefit from the synergistic effect of Co_(3)Se_(4) nanoparticles(highly catalytic ability and strong adsorbability for LiPSs)and the special carbonaceous structure,rapidly converting LiPSs and inhibiting the shuttle of LiPSs.Therefore,lithium-sulfur battery assembled with S/NC@Co_(3)Se_(4)/CNTs cathode as well as nitrogen and sulfur co-doped carbon-coated polypropylene(N,S-C/PP)separator possesses a high initial discharge capacity of 1413 mAh·g-1 at 0.12C and persistently circulates for 1000 cycles at 1C with a capacity attenuation rate per cycle of 0.034%.This work provides a realistic idea for the use of transition metal selenide in the field of high-performance LSBs.
文摘Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.
