The electron interaction among the noncovalently engineered graphene-methylene blue（MB） nanocompo- site with a dipolar pull-push hybrid model was studied. The π-π interaction between reduced graphene oxide（rGO） ...The electron interaction among the noncovalently engineered graphene-methylene blue（MB） nanocompo- site with a dipolar pull-push hybrid model was studied. The π-π interaction between reduced graphene oxide（rGO） and MB molecule was studied by 1HNMR spectroscopy. The electrochemical investigation indicates MB has a stronger electron transfer interaction with rGO than with GO. The ability of graphene-MB nanocomposites to undergo photoinduced electron transfer was confirmed from the capability of the nanocomposites coated electrode to generate photocurrent in a photoelectrochemical cell. The role of graphene as electron acceptor in the opto-electronic assembly was discussed.展开更多
High-frequency magnetic materials are crucial for realizing anti-electromagnetic interference in GHz communication devices and electronic equipment.Current mainstream strategy to enhance highfrequency magnetic losses ...High-frequency magnetic materials are crucial for realizing anti-electromagnetic interference in GHz communication devices and electronic equipment.Current mainstream strategy to enhance highfrequency magnetic losses is shape anisotropy,and it is still difficult to obtain an improvement in intrinsic magnetic loss through electronic structure design.In this paper,the effects of 4f-3d interaction between Er and Fe/Co on magnetic moment,charge migration,and spin polarization were investigated based on density functional theory(DFT).The results show that Er 4f-Fe 3d orbitals undergo significant hybridization at around-4 eV,which increase the electronic locality of Fe and enhance the spin of Fe from 2.86 h/2 to 2.91 h/2.The Fe_(0.5-x)Co_(0.5)Er_(x)(0≤x≤0.05)alloys were further prepared by vacuum induction melting and mechanical alloying methods.The saturation magnetization intensity(Ms)increases from 0.141 to 0.182 A·m^(2)/g with increasing Er content.The μ"of Fe_(0.47)Co_(0.5)Er_(0.03)at 16.7 GHz increases from 0.55 to 0.93,and the frequency range over which tanδ_μvalues are greater than 0.5covers 8.0-18.0 GHz,with the maximum value being 0.83 at 17.0 GHz.These results indicate that the Fe_(0.5-x)Co_(0.5)Er_(x)/paraffin composite materials have excellent high-frequency magnetic losses and are promising candidates in the field of microwave-absorbing materials.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic effic...A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).展开更多
In this article we review recent transport property studies on topological insulator thin films grown by molecular beam epitaxy.In pure Bi2Se3 ultrathin films we find an insulating ground state in the presence of weak...In this article we review recent transport property studies on topological insulator thin films grown by molecular beam epitaxy.In pure Bi2Se3 ultrathin films we find an insulating ground state in the presence of weak antilocalization,which indicates the relevance of electron interaction effect.In magnetically doped Bi2Se3 film we observe a systematic crossover between weak localization and weak antilocalization with varied magnetic doping,temperature,and magnetic field.These results demonstrate the intricate interplay between topological delocalization,electron interaction,and broken time reversal symmetry in topological insulator thin films.展开更多
The efficiency of electrochemical water splitting is extremely hampered by the sluggish oxygen evolution reaction(OER)occurred at the anode.Therefore,developing high-performance OER electrocatalysts is crucial for rea...The efficiency of electrochemical water splitting is extremely hampered by the sluggish oxygen evolution reaction(OER)occurred at the anode.Therefore,developing high-performance OER electrocatalysts is crucial for realizing the industrialized application of water splitting.Herein,a high-efficiency electrocatalyst of ruthenium-decorated nickel-iron hydroxide(10 Ru-NiFe LDH)supported on Ni foam is successfully synthesized for OER.Modifying NiFe LDH with ruthenium can optimize the electronic density to form high valences of metal sites,which is beneficial to promote its OER performance.Consequently,the 10 Ru-NiFe LDH only needs a low overpotential of 222 mV to achieve a current density of50 mA,cm^(-2),which exhibits fast OER kinetics with a small Tafel slope of 58 mV.dec^(-1).Moreover,this electrocatalyst shows high stability over 20 h at a high current density of 100 mA·cm^(-2)without obvious decay.The decent OER performances can be ascribed to the increased active sites and the synergistic electronic interactions among Ni,Fe and Ru.This work provides an effective approach for designing desirable electrocatalysts for OER.展开更多
Lithium-sulfur battery is strongly considered as the most promising next-generation energy storage system because of the high theoretical specific capacity.The serious"shuttle effect"and sluggish reaction ki...Lithium-sulfur battery is strongly considered as the most promising next-generation energy storage system because of the high theoretical specific capacity.The serious"shuttle effect"and sluggish reaction kinetic limited the commercial application of lithium-sulfur battery.Many hetero structure s were applied to accelerate polysulfides conversion and suppress their migration in lithium-sulfur batteries.Nevertheless,the effect of the interface in heterostructure was not clear.Here,the Co_(2)B@MXene heterostructure is synthesized through chemical reactions at room temperature and employed as the interlayer material for Li-S batteries.The theoretical calculations and experimental results indicate that the interfacial electronic interaction of Co_(2)B@MXene induce the transfer of electrons from Co_(2)B to MXene,enhancing the catalytic ability and favoring fast redox kinetics of the polysulfides,and the theoretical calculations also reveal the underlying mechanisms for the electron transfer is that the two materials have different Fermi energy levels.The cell with Co_(2)B@MXene exhibits a high initial capacity of1577 mAh/g at 0.1 C and an ultralow capacity decay of 0.0088%per cycle over 2000 cycles at 2 C.Even at5.1 mg/cm^(2) of sulfur loading,the cell with Co_(2)B@MXene delivers 5.2 mAh/cm^(2) at 0.2 C.展开更多
The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of sin...The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of single Pt atom supported on vacancies in a boron nitride nanosheet.Moreover,the relation between the EMSI and the performance of Pt in propane direct dehydrogenation(PDH)is investigated in detail.The charge state and partial density of states of single Pt atom show distinct features at different anchoring positions,such as boron and nitrogen vacancies(Bvac and Nvac,respectively).Single Pt atom become positively and negatively charged on Bvac and Nvac,respectively.Therefore,the electronic structure of Pt can be adjusted by rational deposition on the support.Moreover,Pt atoms in different charge states have been shown to have different catalytic abilities in PDH.The DFT calculations reveal that Pt atoms on Bvac(Pt-Bvac)have much higher reactivity towards reactant/product adsorption and C–H bond activation than Pt supported on Nvac(Pt-Nvac),with larger adsorption energy and lower barrier along the reaction pathway.However,the high reactivity of Pt-Bvac also hinders propene desorption,which could lead to unwanted deep dehydrogenation.Therefore,the results obtained herein suggest that a balanced reactivity for C–H activation in propane and propene desorption is required to achieve optimum yields.Based on this descriptor,a single Pt atom on a nitrogen vacancy is considered an effective catalyst for PDH.Furthermore,the deep dehydrogenation of the formed propene is significantly suppressed,owing to the large barrier on Pt-Nvac.The current work demonstrates that the catalytic properties of supported single Pt atoms can be tuned by rationally depositing them on a boron nitride nanosheet and highlights the great potential of single-atom catalysis in the PDH reaction.展开更多
For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O{111}and{100}planes were comparatively explored...For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O{111}and{100}planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects.The activity result demonstrates that CeO_(2)/o-Cu_(2)O{111}has superior performance compared with CeO_(2)/c-Cu_(2)O{100}.Credit to the coordination unsaturated copper atoms(Cu_(CUS))on oCu_(2)O{111}surface,the interfacial electronic interactions on CeO_(2)/o-Cu_(2)O{111}are more obvious than those on CeO_(2)/c-Cu_(2)O{100},leading to richer oxygen defect generation,better redox and activation abilities of CO and O_(2)reactants.Furthermore,the reaction mechanism of CeO_(2)/o-Cu_(2)O{111}on CO oxidation is revealed,i.e.,CO and O_(2)are adsorbed on the Cucus on Cu_(2)O{111}and oxygen defect of CeO_(2),respectively,and then synergistically promote the CO oxidation to CO_(2).The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.展开更多
We investigated the properties of polarons in a wurtzite ZnO/MgxZn1-xO quantum well by adopting a modified Lee–Low–Pines variational method, giving the ground state energy, transition energy, and phonon contribution...We investigated the properties of polarons in a wurtzite ZnO/MgxZn1-xO quantum well by adopting a modified Lee–Low–Pines variational method, giving the ground state energy, transition energy, and phonon contributions from various optical-phonon modes to the ground state energy as functions of the well width and Mg composition. In our calculations, we considered the effects of confined optical phonon modes, interface-optical phonon modes, and half-space phonon modes, as well as the anisotropy of the electron effective band mass, phonon frequency, and dielectric constant. Our numerical results indicate that the electron–optical phonon interactions importantly affect the polaronic energies in the ZnO/MgxZn1-xO quantum well. The electron–optical phonon interactions decrease the polaron energies. For quantum wells with narrower wells, the interface optical phonon and half-space phonon modes contribute more to the polaronic energies than the confined phonon modes. However, for wider quantum wells, the total contribution to the polaronic energy mainly comes from the confined modes. The contributions of the various phonon modes to the transition energy change differently with increasing well width. The contribution of the half-space phonons decreases slowly as the QW width increases, whereas the contributions of the confined and interface phonons reach a maximum at d ≈ 5.0 nm and then decrease slowly. However,the total contribution of phonon modes to the transition energy is negative and increases gradually with the QW width of d.As the composition x increases, the total contribution of phonons to the ground state energies increases slowly, but the total contributions of phonons to the transition energies decrease gradually. We analyze the physical reasons for these behaviors in detail.展开更多
Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promisin...Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2) lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2) exhibits superior durability to its counterpart(∼14.6% retention)with 91.1% retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2) is capable of dehydrogenating ethanol at low reaction energies.展开更多
Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The hig...Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.展开更多
Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we ut...Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η_(10) at 288 mV;Tafel slope of 44 mV dec^(-1)),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.展开更多
We investigate the effects of pre-stress and surface tension on the electron–acoustic phonon scattering rate and the mobility of rectangular silicon nanowires. With the elastic theory and the interaction Hamiltonian ...We investigate the effects of pre-stress and surface tension on the electron–acoustic phonon scattering rate and the mobility of rectangular silicon nanowires. With the elastic theory and the interaction Hamiltonian for the deformation potential, which considers both the surface energy and the acoustoelastic effects, the phonon dispersion relation for a stressed nanowire under spatial confinement is derived. The subsequent analysis indicates that both surface tension and pre-stress can dramatically change the electron–acoustic phonon interaction. Under a negative（positive） surface tension and a tensile（compressive） pre-stress, the electron mobility is reduced（enhanced） due to the decrease（increase） of the phonon energy as well as the deformation-potential scattering rate. This study suggests an alternative approach based on the strain engineering to tune the speed and the drive current of low-dimensional electronic devices.展开更多
The transition energies, E1 transitional oscillator strengths of the spin-allowed as well as the spin-forbidden and the corresponding transition rates, and complete M1, E2, M2 forbidden transition rates for 1s^(2), 1s...The transition energies, E1 transitional oscillator strengths of the spin-allowed as well as the spin-forbidden and the corresponding transition rates, and complete M1, E2, M2 forbidden transition rates for 1s^(2), 1s2s, and 1s2p states of He I, are investigated using the multi-configuration Dirac–Hartree–Fock method. In the subsequent relativistic configuration interaction computations, the Breit interaction and the QED effect are considered as perturbation, separately. Our transition energies, oscillator strengths, and transition rates are in good agreement with the experimental and other theoretical results. As a result, the QED effect is not important for helium atoms, however, the effect of the Breit interaction plays a significant role in the transition energies, the oscillator strengths and transition rates.展开更多
We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods includi...We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods including Davidson correction （icMRCIq-Q） with different basis sets aug-cc-pVXZ （X=T, Q, 5）. For the first time, the potential energy curves of electronic states of CF2 related icMRCI＋Q/aug-cc-pVTZ level. The ab initio results will and dynamics of electronic states of CF2 radical. to the lowest dissociation limit are calculated at the further increase our understanding of the structures展开更多
Generation of attosecond electromagnetic （EM） pulses and the associated electron dynamics are studied using particle-in-cell simulations of relativistic laser pulses interacting with over-dense plasma foil targets. ...Generation of attosecond electromagnetic （EM） pulses and the associated electron dynamics are studied using particle-in-cell simulations of relativistic laser pulses interacting with over-dense plasma foil targets. The inter- action process is found to be so complicated even in the situation of utilizing driving laser pulses of only one cycle. Two electron bunches closely involved in the laser-driven wavebreaking process contribute to attosecond EM pulses through the coherent synchrotron emission process whose spectra are found to follow an exponential decay rule. Detailed investigations of electron dynamics indicate that the early part of the reflected EM emission is the high-harmonics produced through the relativistic oscillating mirror mechanism. High harmonics are also found to be generated through the Bremsstrahlung radiation by one electron bunch that participates in the wavebreaking process and decelerates when it experiences the local wavebreaking-generated high electrostatic field in the moving direction.展开更多
Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts f...Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts from Ru-doped NiAl-hydrotalcite using a hydrotherma method.The Ru-Ni-Al catalyst demonstrated much higher activity for CO_(2)methanation than the Ni-Al catalyst that did not have Ru doping Both experimental results and theoretical calculations indicate that the enhanced performance of the Ru-Ni-Al catalyst is related to electroni interactions between nickel(Ni)and ruthenium(Ru).The Ru sites transfer electrons to the Ni sites,increasing the local electron density of Ni which enhances the adsorption and activation of H_(2).Furthermore,the Ru-Ni metal interface sites improve the adsorption and activation of CO_(2)In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)analysis indicates that adjusting the electronic structure of N sites can accelerate the production of intermediates HCOO^(*),while Ru-Ni intermetallic interface sites can directly dissociate CO_(2)into CO^(*).In addition,CO_(2)methanation on the Ru-Ni-Al catalyst follows HCOO^(*)-and CO^(*)-mediated pathways.This study underscores the potential fo enhancing CO_(2)methanation performance by modulating the electronic structure of Ni sites.展开更多
Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy ...Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.展开更多
Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the develop...Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.展开更多
文摘The electron interaction among the noncovalently engineered graphene-methylene blue（MB） nanocompo- site with a dipolar pull-push hybrid model was studied. The π-π interaction between reduced graphene oxide（rGO） and MB molecule was studied by 1HNMR spectroscopy. The electrochemical investigation indicates MB has a stronger electron transfer interaction with rGO than with GO. The ability of graphene-MB nanocomposites to undergo photoinduced electron transfer was confirmed from the capability of the nanocomposites coated electrode to generate photocurrent in a photoelectrochemical cell. The role of graphene as electron acceptor in the opto-electronic assembly was discussed.
基金Project supported by the Nation Natural Science Foundation of China(52304410,51972242)Major Project of Hubei Province(2023BAA003)。
文摘High-frequency magnetic materials are crucial for realizing anti-electromagnetic interference in GHz communication devices and electronic equipment.Current mainstream strategy to enhance highfrequency magnetic losses is shape anisotropy,and it is still difficult to obtain an improvement in intrinsic magnetic loss through electronic structure design.In this paper,the effects of 4f-3d interaction between Er and Fe/Co on magnetic moment,charge migration,and spin polarization were investigated based on density functional theory(DFT).The results show that Er 4f-Fe 3d orbitals undergo significant hybridization at around-4 eV,which increase the electronic locality of Fe and enhance the spin of Fe from 2.86 h/2 to 2.91 h/2.The Fe_(0.5-x)Co_(0.5)Er_(x)(0≤x≤0.05)alloys were further prepared by vacuum induction melting and mechanical alloying methods.The saturation magnetization intensity(Ms)increases from 0.141 to 0.182 A·m^(2)/g with increasing Er content.The μ"of Fe_(0.47)Co_(0.5)Er_(0.03)at 16.7 GHz increases from 0.55 to 0.93,and the frequency range over which tanδ_μvalues are greater than 0.5covers 8.0-18.0 GHz,with the maximum value being 0.83 at 17.0 GHz.These results indicate that the Fe_(0.5-x)Co_(0.5)Er_(x)/paraffin composite materials have excellent high-frequency magnetic losses and are promising candidates in the field of microwave-absorbing materials.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金supported by the Natural Scientific Foundation of China(Nos.22127803,22174110,22203050)Natural Scientific Foundation of Shandong(No.ZR2022QB002)China Postdoctoral Science Foundation(No.2020T130331)。
文摘A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).
基金supported by the National Natural Science Foundation of China(Grant Nos.10834003,10911130233)the Ministry of Science and Technology of China(Grant No.2009CB929400)the Chinese Academy of Sciences
文摘In this article we review recent transport property studies on topological insulator thin films grown by molecular beam epitaxy.In pure Bi2Se3 ultrathin films we find an insulating ground state in the presence of weak antilocalization,which indicates the relevance of electron interaction effect.In magnetically doped Bi2Se3 film we observe a systematic crossover between weak localization and weak antilocalization with varied magnetic doping,temperature,and magnetic field.These results demonstrate the intricate interplay between topological delocalization,electron interaction,and broken time reversal symmetry in topological insulator thin films.
基金financially supported by the National Natural Science Foundation of China (Nos.12074435, 51871250 and 52001335)the Science and Technology Innovation Program of Hunan Province (No.2021RC4001)the State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metal (No.SKL-SPM-202005)
文摘The efficiency of electrochemical water splitting is extremely hampered by the sluggish oxygen evolution reaction(OER)occurred at the anode.Therefore,developing high-performance OER electrocatalysts is crucial for realizing the industrialized application of water splitting.Herein,a high-efficiency electrocatalyst of ruthenium-decorated nickel-iron hydroxide(10 Ru-NiFe LDH)supported on Ni foam is successfully synthesized for OER.Modifying NiFe LDH with ruthenium can optimize the electronic density to form high valences of metal sites,which is beneficial to promote its OER performance.Consequently,the 10 Ru-NiFe LDH only needs a low overpotential of 222 mV to achieve a current density of50 mA,cm^(-2),which exhibits fast OER kinetics with a small Tafel slope of 58 mV.dec^(-1).Moreover,this electrocatalyst shows high stability over 20 h at a high current density of 100 mA·cm^(-2)without obvious decay.The decent OER performances can be ascribed to the increased active sites and the synergistic electronic interactions among Ni,Fe and Ru.This work provides an effective approach for designing desirable electrocatalysts for OER.
基金supported by the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.2019DX13)。
文摘Lithium-sulfur battery is strongly considered as the most promising next-generation energy storage system because of the high theoretical specific capacity.The serious"shuttle effect"and sluggish reaction kinetic limited the commercial application of lithium-sulfur battery.Many hetero structure s were applied to accelerate polysulfides conversion and suppress their migration in lithium-sulfur batteries.Nevertheless,the effect of the interface in heterostructure was not clear.Here,the Co_(2)B@MXene heterostructure is synthesized through chemical reactions at room temperature and employed as the interlayer material for Li-S batteries.The theoretical calculations and experimental results indicate that the interfacial electronic interaction of Co_(2)B@MXene induce the transfer of electrons from Co_(2)B to MXene,enhancing the catalytic ability and favoring fast redox kinetics of the polysulfides,and the theoretical calculations also reveal the underlying mechanisms for the electron transfer is that the two materials have different Fermi energy levels.The cell with Co_(2)B@MXene exhibits a high initial capacity of1577 mAh/g at 0.1 C and an ultralow capacity decay of 0.0088%per cycle over 2000 cycles at 2 C.Even at5.1 mg/cm^(2) of sulfur loading,the cell with Co_(2)B@MXene delivers 5.2 mAh/cm^(2) at 0.2 C.
基金supported by the National Science Foundation of China(91545117)the Natural Science Foundation of Liaoning Province(201602676)+1 种基金the Fundamental Research Funds for Colleges and Universities in Liaoning Province(LQN201703)the Startup Foundation for Doctors of Shenyang Normal University(BS201620)~~
文摘The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of single Pt atom supported on vacancies in a boron nitride nanosheet.Moreover,the relation between the EMSI and the performance of Pt in propane direct dehydrogenation(PDH)is investigated in detail.The charge state and partial density of states of single Pt atom show distinct features at different anchoring positions,such as boron and nitrogen vacancies(Bvac and Nvac,respectively).Single Pt atom become positively and negatively charged on Bvac and Nvac,respectively.Therefore,the electronic structure of Pt can be adjusted by rational deposition on the support.Moreover,Pt atoms in different charge states have been shown to have different catalytic abilities in PDH.The DFT calculations reveal that Pt atoms on Bvac(Pt-Bvac)have much higher reactivity towards reactant/product adsorption and C–H bond activation than Pt supported on Nvac(Pt-Nvac),with larger adsorption energy and lower barrier along the reaction pathway.However,the high reactivity of Pt-Bvac also hinders propene desorption,which could lead to unwanted deep dehydrogenation.Therefore,the results obtained herein suggest that a balanced reactivity for C–H activation in propane and propene desorption is required to achieve optimum yields.Based on this descriptor,a single Pt atom on a nitrogen vacancy is considered an effective catalyst for PDH.Furthermore,the deep dehydrogenation of the formed propene is significantly suppressed,owing to the large barrier on Pt-Nvac.The current work demonstrates that the catalytic properties of supported single Pt atoms can be tuned by rationally depositing them on a boron nitride nanosheet and highlights the great potential of single-atom catalysis in the PDH reaction.
基金Project supported by the National Natural Science Foundation of China(21707066,21677069)。
文摘For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O{111}and{100}planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects.The activity result demonstrates that CeO_(2)/o-Cu_(2)O{111}has superior performance compared with CeO_(2)/c-Cu_(2)O{100}.Credit to the coordination unsaturated copper atoms(Cu_(CUS))on oCu_(2)O{111}surface,the interfacial electronic interactions on CeO_(2)/o-Cu_(2)O{111}are more obvious than those on CeO_(2)/c-Cu_(2)O{100},leading to richer oxygen defect generation,better redox and activation abilities of CO and O_(2)reactants.Furthermore,the reaction mechanism of CeO_(2)/o-Cu_(2)O{111}on CO oxidation is revealed,i.e.,CO and O_(2)are adsorbed on the Cucus on Cu_(2)O{111}and oxygen defect of CeO_(2),respectively,and then synergistically promote the CO oxidation to CO_(2).The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11264027 and 11364030)the Project of Prairie Excellent Specialist of Inner Mongolia,Chinathe "Thousand,Hundred and Ten" Talent Training Project Foundation of Inner Mongolia Normal University,China(Grant No.RCPY-2-2012-K-039)
文摘We investigated the properties of polarons in a wurtzite ZnO/MgxZn1-xO quantum well by adopting a modified Lee–Low–Pines variational method, giving the ground state energy, transition energy, and phonon contributions from various optical-phonon modes to the ground state energy as functions of the well width and Mg composition. In our calculations, we considered the effects of confined optical phonon modes, interface-optical phonon modes, and half-space phonon modes, as well as the anisotropy of the electron effective band mass, phonon frequency, and dielectric constant. Our numerical results indicate that the electron–optical phonon interactions importantly affect the polaronic energies in the ZnO/MgxZn1-xO quantum well. The electron–optical phonon interactions decrease the polaron energies. For quantum wells with narrower wells, the interface optical phonon and half-space phonon modes contribute more to the polaronic energies than the confined phonon modes. However, for wider quantum wells, the total contribution to the polaronic energy mainly comes from the confined modes. The contributions of the various phonon modes to the transition energy change differently with increasing well width. The contribution of the half-space phonons decreases slowly as the QW width increases, whereas the contributions of the confined and interface phonons reach a maximum at d ≈ 5.0 nm and then decrease slowly. However,the total contribution of phonon modes to the transition energy is negative and increases gradually with the QW width of d.As the composition x increases, the total contribution of phonons to the ground state energies increases slowly, but the total contributions of phonons to the transition energies decrease gradually. We analyze the physical reasons for these behaviors in detail.
基金Key Research and Development Program of Zhejiang,Grant/Award Number:2021C03022National Natural Science Foundation of China,Grant/Award Numbers:22002104,22272115,22202145,22202146,22102112,22202147。
文摘Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2) lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2) exhibits superior durability to its counterpart(∼14.6% retention)with 91.1% retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2) is capable of dehydrogenating ethanol at low reaction energies.
基金the National Natural Science Foundation of China (22108189, 22278286)Science Foundation for Distinguished Young Scholar of Shanxi Province(202303021223001)SINOPEC 122027
文摘Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.
基金The work was supported by the National Natural Science Foundation of China(52372174)Carbon Neutrality Research Institute Fund(CNIF20230204)Special Project of Strategic Cooperation between China National Petroleum Corporation and China University of Petroleum(Beijing)(ZLZX-2020-04).
文摘Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η_(10) at 288 mV;Tafel slope of 44 mV dec^(-1)),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11472243,11302189,and 11321202)the Doctoral Fund of Ministry of Education of China(Grant No.20130101120175)+1 种基金the Zhejiang Provincial Qianjiang Talent Program,China(Grant No.QJD1202012)the Educational Commission of Zhejiang Province,China(Grant No.Y201223476)
文摘We investigate the effects of pre-stress and surface tension on the electron–acoustic phonon scattering rate and the mobility of rectangular silicon nanowires. With the elastic theory and the interaction Hamiltonian for the deformation potential, which considers both the surface energy and the acoustoelastic effects, the phonon dispersion relation for a stressed nanowire under spatial confinement is derived. The subsequent analysis indicates that both surface tension and pre-stress can dramatically change the electron–acoustic phonon interaction. Under a negative（positive） surface tension and a tensile（compressive） pre-stress, the electron mobility is reduced（enhanced） due to the decrease（increase） of the phonon energy as well as the deformation-potential scattering rate. This study suggests an alternative approach based on the strain engineering to tune the speed and the drive current of low-dimensional electronic devices.
基金Supported by the National Key Research and Development Program of China (Grant No. 2017YFA0402300)the National Natural Science Foundation of China (Grant Nos. 11774344 and 11474033)。
文摘The transition energies, E1 transitional oscillator strengths of the spin-allowed as well as the spin-forbidden and the corresponding transition rates, and complete M1, E2, M2 forbidden transition rates for 1s^(2), 1s2s, and 1s2p states of He I, are investigated using the multi-configuration Dirac–Hartree–Fock method. In the subsequent relativistic configuration interaction computations, the Breit interaction and the QED effect are considered as perturbation, separately. Our transition energies, oscillator strengths, and transition rates are in good agreement with the experimental and other theoretical results. As a result, the QED effect is not important for helium atoms, however, the effect of the Breit interaction plays a significant role in the transition energies, the oscillator strengths and transition rates.
基金Supported by the 2014 Postdoctoral Sustentation Fund of Qingdao under Grant No 01020120517the Natural Science Foundation of Shandong Province under Grant No ZR2014AP001+1 种基金the National Natural Science Foundation of China under Grant No11447226the Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents under Grant No 2015RCJJ015
文摘We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods including Davidson correction （icMRCIq-Q） with different basis sets aug-cc-pVXZ （X=T, Q, 5）. For the first time, the potential energy curves of electronic states of CF2 related icMRCI＋Q/aug-cc-pVTZ level. The ab initio results will and dynamics of electronic states of CF2 radical. to the lowest dissociation limit are calculated at the further increase our understanding of the structures
基金Supported by the National Natural Science Foundation of China under Grant No 11674146the National Basic Research Program of China under Grant No 2013CBA01500
文摘Generation of attosecond electromagnetic （EM） pulses and the associated electron dynamics are studied using particle-in-cell simulations of relativistic laser pulses interacting with over-dense plasma foil targets. The inter- action process is found to be so complicated even in the situation of utilizing driving laser pulses of only one cycle. Two electron bunches closely involved in the laser-driven wavebreaking process contribute to attosecond EM pulses through the coherent synchrotron emission process whose spectra are found to follow an exponential decay rule. Detailed investigations of electron dynamics indicate that the early part of the reflected EM emission is the high-harmonics produced through the relativistic oscillating mirror mechanism. High harmonics are also found to be generated through the Bremsstrahlung radiation by one electron bunch that participates in the wavebreaking process and decelerates when it experiences the local wavebreaking-generated high electrostatic field in the moving direction.
基金support from the National Natural Science Foundation of China(22278006)Open Project Fund from Guangdong Provincial Key Laboratory of Materials and Technology for Energy Conversion,Guangdong Technion-Israel Institute of Technology(MATEC2024KF009)Open Research Fund of State Key Laboratory of Mesoscience and Engineering(MESO-23-D13)。
文摘Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts from Ru-doped NiAl-hydrotalcite using a hydrotherma method.The Ru-Ni-Al catalyst demonstrated much higher activity for CO_(2)methanation than the Ni-Al catalyst that did not have Ru doping Both experimental results and theoretical calculations indicate that the enhanced performance of the Ru-Ni-Al catalyst is related to electroni interactions between nickel(Ni)and ruthenium(Ru).The Ru sites transfer electrons to the Ni sites,increasing the local electron density of Ni which enhances the adsorption and activation of H_(2).Furthermore,the Ru-Ni metal interface sites improve the adsorption and activation of CO_(2)In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)analysis indicates that adjusting the electronic structure of N sites can accelerate the production of intermediates HCOO^(*),while Ru-Ni intermetallic interface sites can directly dissociate CO_(2)into CO^(*).In addition,CO_(2)methanation on the Ru-Ni-Al catalyst follows HCOO^(*)-and CO^(*)-mediated pathways.This study underscores the potential fo enhancing CO_(2)methanation performance by modulating the electronic structure of Ni sites.
基金supported by the National Natural Science Foundation of China(52363028,21965005)the Natural Science Foundation of Guangxi Province(2021GXNSFAA076001)the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20297039)。
文摘Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.
基金the financial support of Guangdong Basic and Applied Basic Research Foundation (No. 2023A1515010940)Shenzhen Natural Science Fund (the Stable Support Plan Program No. 20220809160022001)the Shenzhen Science and Technology Programs (No. ZDSYS20220527171401003, KQTD20190929173914967)。
文摘Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.
