The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere f...The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.展开更多
Amorphous transition metal compounds(a-TMC)become one of the most promising pre-catalysts toward oxygen evolution reaction(OER)due to their high-entropy nature and flexible self-reconstruction to highly active derivat...Amorphous transition metal compounds(a-TMC)become one of the most promising pre-catalysts toward oxygen evolution reaction(OER)due to their high-entropy nature and flexible self-reconstruction to highly active derivatives.However,the loosen bonds inside the amorphous structure make it an electronic insulator with unstable structure.Here,monodispersed Ni^(2+)-phytate nanospheres implanted by Fe^(3+)ions(NS_(FeNiPA))were firstly prepared and subsequently transferred into homogeneous high-entropy type Fe-Ni-P-O-C amorphous nanospheres(CNS_(FeNiPO)).It is shown that the CNS_(FeNiPO) presents robust structure and remarkable Fe ions migration during potential-driven activation process,which benefits efficient surface reconstruction and spherical morphology preservation.The CNS_(FeNiPO) with low mass loading of 0.1mg/cm^(2)could deliver small overpotential of 270mV at 10mAcm^(−2)and almost 100%retention of the initial current density after 10h test.The improved electrocatalytic activity is attributed to the boosted electron transfer from Ni sites to O-containing intermediates by introduction of Fe and P atoms.Moreover,rechargeable Zn-air battery with CNS_(FeNiPO)+Pt/C could achieve lower charge potential platform and better cycling performance than that with commercial RuO_(2)+Pt/C.This work provides new insights into the design and understanding of high-entropy amorphous pre-catalysts toward OER.展开更多
The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorpti...The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorption and H-OH dissociative adsorption are revealed by our calculations. The activities of the surface reactions of H2O on GaN（0001） surface are investigated. For the stepwise processes of H2O decomposition into H2 in gas phase and adsorbed O atom （H2O（g）→H2O（chem）→OH（chem） ＋ H（chem）→2H（chem） ＋ O（chem）→H2（g） ＋ O（chem））, the first and second steps are facile and can even occur at room temperature; while the last two have high barriers and thus are difficult to proceed, especially the fourth step is endothermic. In short, H2O adsorption and decomposition into H2 in gas phase and adsorbed O atom on GaN（0001） surface are exothermic by -43.98 kcal/mol.展开更多
Pt-Ni alloy nanocrystals with Pt-enriched shells were prepared by selective etching of surface Ni using sulfuric acid and hydroquinone.The changes in the electronic and geometric structure of the alloy nanoparticles a...Pt-Ni alloy nanocrystals with Pt-enriched shells were prepared by selective etching of surface Ni using sulfuric acid and hydroquinone.The changes in the electronic and geometric structure of the alloy nanoparticles at the surface were elucidated from the electrochemical surface area,the potential of zero total charge(PZTC),and relative surface roughness,which were determined from CO-and CO_(2)-displacement experiments before and after 3000 potential cycles under oxygen reduction reaction conditions.While the highest activity and durability were achieved in hydroquinone-treated Pt–Ni,sulfuric acidtreated one showed the lower activity and durability despite its higher surface Pt concentration and alloying level.Both PZTC and QCO_(2)/QCO ratio(desorption charge of reductively adsorbed CO_(2) normalized by COad-stripping charge)depend on surface roughness.In particular,QCO_(2)/QCO ratio change better reflects the roughness on an atomic scale,and PZTC is also affected by the electronic modification of Pt atoms in surface layers.In this study,a comparative study is presented to find a relationship between surface structure and electrochemical properties,which reveals that surface roughness plays a critical role to improve the electrochemical performance of Pt-Ni alloy catalysts with Pt-rich surfaces.展开更多
The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction me...The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.展开更多
We demonstrate a process to achieve selective surface metallization of ZrO_(2)ceramics using ultrasound technology in atmospheric environments at 350℃,which bestows good weldability of ZrO_(2)to achieve rapid and rel...We demonstrate a process to achieve selective surface metallization of ZrO_(2)ceramics using ultrasound technology in atmospheric environments at 350℃,which bestows good weldability of ZrO_(2)to achieve rapid and reliable connections with other metals as well as ceramic materials.The challenge is that brazing or diffusion welding processes to accomplish metallurgical connections for ZrO_(2) typically require holding at elevated temperatures for minutes to hours,while the selective ultrasonic metallization process requires only a few seconds of processing without the application of covering films or solder resists.In this study,the selected Sn-2Ti alloy could effectively wet and spread on ZrO_(2)substrate under ultrasonication,and continuous interphase layers were rapidly formed in situ between ZrO_(2)and Sn-2Ti.The bonding strength for the ZrO_(2)/Sn-2Ti interface was well established with the highest shear strength of 37.1 MPa,and the fracture location occurred at the filler metal.The interfacial reaction layer thickened remarkably with the prolongation of sonication,accompanied by the partial crystallization of amorphous TiO and the formation of irregularly striped Ti_(11.31)Sn_(3)O_(10)nanocrystals.展开更多
Developing efficient oxygen evolution reaction(OER) electrocatalysts such as transition metal sulfides(TMSs) is of great importance to advance renewable hydrogen fuel toward further practical applications.Herein,NiCoS...Developing efficient oxygen evolution reaction(OER) electrocatalysts such as transition metal sulfides(TMSs) is of great importance to advance renewable hydrogen fuel toward further practical applications.Herein,NiCoS_(2) nanoparticles well decorated on double-sided N-doped reduced graphene oxide sheets(NiCoS_(2)/rGO) are prepared from an Al-containing ternary NiCoAl-layered double hydroxide precursor(NiCoAl-LDH) grown on GO support as an OER electrocatalyst.The Al-confinementassisted sulfurization,followed by selective acid treatment,endows the resulting NiCoS_(2)/rGO composite with the advantages:well-dispersed NiCoS_(2) nanoparticles,dualsided rGO support,as well as a large specific surface area of 119.4 m^(2)·g^(-1) and meso-/macroporous size distribution.The NiCoS_(2)/rGO electrocatalyst exhibits an overpotential of 273 mV at 10 mA·cm^(-2) and a good stability of 24 h,which outperform those of the counterparts of NiS_(2)/rGO and CoS_(2)/rGO.The results of electrochemical active surface area and electrochemical impedance spectra experimentally provide convincing rationales of the information of active sites and good conductivity,both underpin the enhanced electrocatalytic performances.展开更多
Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-a...Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-active properties, whereas the large-area basal plane is inactive.Therefore, recent studies and methodologies have been investigated to improve the performance of TMD-based materials by activating inactive sites through elemental doping strategies. In this review,we focus on the metal and non-metal dopant effects on group VI TMDs such as MoS_(2) MoSe_(2) WS_(2)and WSe_(2) for promoting HER performances in acidic electrolytes. A general introduction to the HER is initially provided to explain the parameters in accessing the catalytic performance of dopedTMDs. Then, synthetic methods for doped-TMDs and their HER performances are introduced in order to understand the effect of various dopants including metallic and non-metallic elements. Finally, the current challenges and future opportunities are summarized to provide insights into developing highly active and stable doped-TMD materials and valuable guidelines for engineering TMD-based nanocatalysts for practical water splitting technologies.展开更多
Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy convers...Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.展开更多
Atomic surfaces are strictly required by high-performance devices of diamond.Nevertheless,diamond is the hardest material in nature,leading to the low material removal rate(MRR)and high surface roughness during machin...Atomic surfaces are strictly required by high-performance devices of diamond.Nevertheless,diamond is the hardest material in nature,leading to the low material removal rate(MRR)and high surface roughness during machining.Noxious slurries are widely used in conventional chemical mechanical polishing(CMP),resulting in the possible pollution to the environment.Moreover,the traditional slurries normally contain more than four ingredients,causing difficulties to control the process and quality of CMP.To solve these challenges,a novel green CMP for single crystal diamond was developed,consisting of only hydrogen peroxide,diamond abrasive and Prussian blue(PB)/titania catalyst.After CMP,atomic surface is achieved with surface roughness Sa of 0.079 nm,and the MRR is 1168 nm·h^(-1).Thickness of damaged layer is merely 0.66 nm confirmed by transmission electron microscopy(TEM).X-ray photoelectron spectroscopy,electron paramagnetic resonance and TEM reveal that·OH radicals form under ultraviolet irradiation on PB/titania catalyst.The·OH radicals oxidize diamond,transforming it from monocrystalline to amorphous atomic structure,generating a soft amorphous layer.This contributes the high MRR and formation of atomic surface on diamond.The developed novel green CMP offers new insights to achieve atomic surface of diamond for potential use in their high-performance devices.展开更多
The kinetics of the surface reactions of single crystal Ni3Al and polycrystal line Ni3Al0.00052 wt% B with water vapor or oxygen was investigated using XPS. Both reactions initiate at less than 1.5×10-6 Pa.s expo...The kinetics of the surface reactions of single crystal Ni3Al and polycrystal line Ni3Al0.00052 wt% B with water vapor or oxygen was investigated using XPS. Both reactions initiate at less than 1.5×10-6 Pa.s exposure. The reaction of Ni3Al does not saturote with water vapor at 0.43 Pa.s; with oxygen at 8.4×10-2 Pa.s and the oxide formed is Al2O3. The kinetics of these reactions can be used to eaplain the different ductility behavior of Ni3Al-based alloys in various environment.展开更多
The interaction of water vapor and oxygen with TiAI-based alloy has been studied with Auger electron spectroscopy and X-ray photoelectron spectroscopy. The results indicate that both surface reactions initiate at a ve...The interaction of water vapor and oxygen with TiAI-based alloy has been studied with Auger electron spectroscopy and X-ray photoelectron spectroscopy. The results indicate that both surface reactions initiate at a very short exposure (about 6×10-7 Pa·s) and the oxides Al2O3 and TiO2 form in the surface reactions. In the oxidizing reaction, the water vapor reacts firstly with Al, and then reacts with Ti after certain exposure. The surface reaction of Al with water vapor may be responsible for the environmental embrittlement at room temperature in TiAI-based alloy.展开更多
A simulation study was carried out by using dissipative particle dynamics(DPD) method to explore the effects of properties of coating chains, such as length, density, rigidity of polymer chains, as well as the distanc...A simulation study was carried out by using dissipative particle dynamics(DPD) method to explore the effects of properties of coating chains, such as length, density, rigidity of polymer chains, as well as the distance between nanoparticles on bonding reaction of coating chains grafted onto nanoparticles. The results show that bonding ratios of coated chains strongly depend on the length and density of coating chains. For nanoparticles with different coating densities, the optimum chain length for bonding reaction are varied. The rigidity of coating chains exhibits vigorous effects on bonding reaction that highly depends on chain lengths. DPD simulation can be used to study the bonding reaction between coated nanoparticles, which may help experimental synthesis of nanocomposites with excellent properties.展开更多
Bimetallic Pt-based catalysts have been extensively investigated to enhance the performance of direct methanol fuel cells(DMFCs) because CO, a by-product, reduces the activity of the pure Pt catalysts. Herein, we synt...Bimetallic Pt-based catalysts have been extensively investigated to enhance the performance of direct methanol fuel cells(DMFCs) because CO, a by-product, reduces the activity of the pure Pt catalysts. Herein, we synthesized Pt-Pb hexagonal nanoplates as a model catalyst for the methanol oxidation reaction(MOR) and further controlled the Pt and Pb distributions on the surface of the nanoplates through acetic acid(HAc) treatment. As a result, we obtained Pt-Pb nanoplates and HAc-treated Pt-Pb nanoplates with homogeneous and heterogeneous distributions of the Pt-Pb alloy surfaces, respectively. We showed that the MOR activity and stability of the Pt-Pb nanoplates improved compared to those of the HAc-treated Pt-Pb nanoplates, mainly due to the enhanced CO tolerance and the modified electronic structure of Pt under the influence of the oxophilic Pb.展开更多
Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogen...Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography（XCT） and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional（3-D） rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy（FE-SEM） to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.展开更多
Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydrox...Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH<span style="white-space:nowrap;">• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH<span style="white-space:nowrap;">• radicals are determined by the energies E<sub>orb</sub> of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |E<sub>orb</sub>|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.展开更多
The effect of boron doping on the sensitivity to environmental embrittlement of Ni3Al-based alloys was investigated in this paper. The results show that the ductilizing effect of boron in Ni3Al is partly to suppress ...The effect of boron doping on the sensitivity to environmental embrittlement of Ni3Al-based alloys was investigated in this paper. The results show that the ductilizing effect of boron in Ni3Al is partly to suppress moisture-induced hydrogen embrittlement.The mechanism of this suppressing effect of boron relates to its severely decreasing the hydrogen diffusivity by boron segregated at the grain boundaries. The surface reaction of Fe3Al with water vapor and oxygen was experimentally confirmed by AES and XPS analysis. The kinetics of these reactions can be used to explain the different ductility behavior of aluminides in various environments.展开更多
Development of reaction-tailored electrocatalysts is becoming increasingly important as energy and environment are among key issues governing our sustainable future.Electrocatalysts are inherently optimized for applic...Development of reaction-tailored electrocatalysts is becoming increasingly important as energy and environment are among key issues governing our sustainable future.Electrocatalysts are inherently optimized for application towards reactions of interest in renewable energy,such as those involved in water splitting and artificial photosynthesis,owing to its energy efficiency,simple fabrication,and ease of operation.In this view,it is important to secure logical design principles for the synthesis of electrocatalysts for various reactions of interest,and also understand their catalytic mechanisms in the respective reactions for improvements in further iterations.In this review,we introduce several key methods of scanning electrochemical microscopy(SECM)in its applications towards electrocatalysis.A brief history and a handful of seminal works in the SECM field is introduced in advancing the synthetic designs of electrocatalysts and elucidation of the operating mechanism.New developments in nano-sizing of the electrodes in attempts for improved spatial resolution of SECM is also introduced,and the application of nanoelectrodes towards the investigation of formerly inaccessible single catalytic entities is shared.展开更多
The partial potential energy surface of the I ＋ HI →IH ＋ I reaction involving the translational and vibrational motions has been constructed at the QCISD（ T ）//MP4SDQ level with the pseudo potential method that i...The partial potential energy surface of the I ＋ HI →IH ＋ I reaction involving the translational and vibrational motions has been constructed at the QCISD（ T ）//MP4SDQ level with the pseudo potential method that is helpful to interpreting the scattering resonance states. The lifetimes of the scattering resonance states in the title reaction obtained from the partial potential energy surface are about 90-120 fs, which agrees with the result of high-resolved threshold photodetachment spectroscopy of anion IHI^- measured by Neumark.展开更多
基金supported by the National Key Research and Development Program of China(2022YFB3805600,2022YFB3805604)the National Natural Science Foundation of China(52201286)+3 种基金the National 111 Project(B20002)the Key R&D Program of Shandong Province,China(2023CXGC010314)the Hubei Provincial Natural Science Foundation of China(2024AFB195)the Fundamental Research Funds for the Central Universities(104972025KFYzxk0014,104972024KFYjlb0008)。
文摘The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.
基金financially supported by National Natural Science Foundation of China(22278170,52172058)Natural Science Foundation of Anhui Province(2408085QB037)+3 种基金Natural Science Foundation of Anhui Provincial Department of Education(2023AH020042,2024AH051721)financial support from High-Level Talents Introduction and Cultivation Plan of Anhui Province-Young Top Talent,Huainan Innovation and Entrepreneurship Star Team(HNSTD-2024),Huainan Research Center of New Carbon Energy Materials(HNSPT02)New Energy Materials and Technology Research Center of Huainan Normal University.Business Finland,BATCircle2.0 project(Grant No.44612/31/2020)is acknowledged for financial supportU.L.acknowledges Finnish Research Impact Foundation for Tandem Industry Academy Professorship funding in 2023-2025.
文摘Amorphous transition metal compounds(a-TMC)become one of the most promising pre-catalysts toward oxygen evolution reaction(OER)due to their high-entropy nature and flexible self-reconstruction to highly active derivatives.However,the loosen bonds inside the amorphous structure make it an electronic insulator with unstable structure.Here,monodispersed Ni^(2+)-phytate nanospheres implanted by Fe^(3+)ions(NS_(FeNiPA))were firstly prepared and subsequently transferred into homogeneous high-entropy type Fe-Ni-P-O-C amorphous nanospheres(CNS_(FeNiPO)).It is shown that the CNS_(FeNiPO) presents robust structure and remarkable Fe ions migration during potential-driven activation process,which benefits efficient surface reconstruction and spherical morphology preservation.The CNS_(FeNiPO) with low mass loading of 0.1mg/cm^(2)could deliver small overpotential of 270mV at 10mAcm^(−2)and almost 100%retention of the initial current density after 10h test.The improved electrocatalytic activity is attributed to the boosted electron transfer from Ni sites to O-containing intermediates by introduction of Fe and P atoms.Moreover,rechargeable Zn-air battery with CNS_(FeNiPO)+Pt/C could achieve lower charge potential platform and better cycling performance than that with commercial RuO_(2)+Pt/C.This work provides new insights into the design and understanding of high-entropy amorphous pre-catalysts toward OER.
基金Supported by the National Natural Science Foundation of China (No. 20673019)
文摘The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorption and H-OH dissociative adsorption are revealed by our calculations. The activities of the surface reactions of H2O on GaN（0001） surface are investigated. For the stepwise processes of H2O decomposition into H2 in gas phase and adsorbed O atom （H2O（g）→H2O（chem）→OH（chem） ＋ H（chem）→2H（chem） ＋ O（chem）→H2（g） ＋ O（chem））, the first and second steps are facile and can even occur at room temperature; while the last two have high barriers and thus are difficult to proceed, especially the fourth step is endothermic. In short, H2O adsorption and decomposition into H2 in gas phase and adsorbed O atom on GaN（0001） surface are exothermic by -43.98 kcal/mol.
基金This study was supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.2019R1F1A1062193).
文摘Pt-Ni alloy nanocrystals with Pt-enriched shells were prepared by selective etching of surface Ni using sulfuric acid and hydroquinone.The changes in the electronic and geometric structure of the alloy nanoparticles at the surface were elucidated from the electrochemical surface area,the potential of zero total charge(PZTC),and relative surface roughness,which were determined from CO-and CO_(2)-displacement experiments before and after 3000 potential cycles under oxygen reduction reaction conditions.While the highest activity and durability were achieved in hydroquinone-treated Pt–Ni,sulfuric acidtreated one showed the lower activity and durability despite its higher surface Pt concentration and alloying level.Both PZTC and QCO_(2)/QCO ratio(desorption charge of reductively adsorbed CO_(2) normalized by COad-stripping charge)depend on surface roughness.In particular,QCO_(2)/QCO ratio change better reflects the roughness on an atomic scale,and PZTC is also affected by the electronic modification of Pt atoms in surface layers.In this study,a comparative study is presented to find a relationship between surface structure and electrochemical properties,which reveals that surface roughness plays a critical role to improve the electrochemical performance of Pt-Ni alloy catalysts with Pt-rich surfaces.
基金Supported by the Joint Funds of the National Natural Science Foundation of China(No.u0837604) the Funds for Applied Basic Researches of Yunnan Province(No.2010CD022)
文摘The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.
基金financially supported by the National Natural Science Foundation of China(No.51805111).
文摘We demonstrate a process to achieve selective surface metallization of ZrO_(2)ceramics using ultrasound technology in atmospheric environments at 350℃,which bestows good weldability of ZrO_(2)to achieve rapid and reliable connections with other metals as well as ceramic materials.The challenge is that brazing or diffusion welding processes to accomplish metallurgical connections for ZrO_(2) typically require holding at elevated temperatures for minutes to hours,while the selective ultrasonic metallization process requires only a few seconds of processing without the application of covering films or solder resists.In this study,the selected Sn-2Ti alloy could effectively wet and spread on ZrO_(2)substrate under ultrasonication,and continuous interphase layers were rapidly formed in situ between ZrO_(2)and Sn-2Ti.The bonding strength for the ZrO_(2)/Sn-2Ti interface was well established with the highest shear strength of 37.1 MPa,and the fracture location occurred at the filler metal.The interfacial reaction layer thickened remarkably with the prolongation of sonication,accompanied by the partial crystallization of amorphous TiO and the formation of irregularly striped Ti_(11.31)Sn_(3)O_(10)nanocrystals.
基金financially supported by the National Natural Science Foundation of China(No.U1607128)。
文摘Developing efficient oxygen evolution reaction(OER) electrocatalysts such as transition metal sulfides(TMSs) is of great importance to advance renewable hydrogen fuel toward further practical applications.Herein,NiCoS_(2) nanoparticles well decorated on double-sided N-doped reduced graphene oxide sheets(NiCoS_(2)/rGO) are prepared from an Al-containing ternary NiCoAl-layered double hydroxide precursor(NiCoAl-LDH) grown on GO support as an OER electrocatalyst.The Al-confinementassisted sulfurization,followed by selective acid treatment,endows the resulting NiCoS_(2)/rGO composite with the advantages:well-dispersed NiCoS_(2) nanoparticles,dualsided rGO support,as well as a large specific surface area of 119.4 m^(2)·g^(-1) and meso-/macroporous size distribution.The NiCoS_(2)/rGO electrocatalyst exhibits an overpotential of 273 mV at 10 mA·cm^(-2) and a good stability of 24 h,which outperform those of the counterparts of NiS_(2)/rGO and CoS_(2)/rGO.The results of electrochemical active surface area and electrochemical impedance spectra experimentally provide convincing rationales of the information of active sites and good conductivity,both underpin the enhanced electrocatalytic performances.
基金supported by the National Research Foundation of Korea(NRF-2021R1A2C4001411,2020R1A4A1018393,2020R1C1C 1008514,2020R1I1A1A01072100,2019R1A6A1A11053838)。
文摘Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-active properties, whereas the large-area basal plane is inactive.Therefore, recent studies and methodologies have been investigated to improve the performance of TMD-based materials by activating inactive sites through elemental doping strategies. In this review,we focus on the metal and non-metal dopant effects on group VI TMDs such as MoS_(2) MoSe_(2) WS_(2)and WSe_(2) for promoting HER performances in acidic electrolytes. A general introduction to the HER is initially provided to explain the parameters in accessing the catalytic performance of dopedTMDs. Then, synthetic methods for doped-TMDs and their HER performances are introduced in order to understand the effect of various dopants including metallic and non-metallic elements. Finally, the current challenges and future opportunities are summarized to provide insights into developing highly active and stable doped-TMD materials and valuable guidelines for engineering TMD-based nanocatalysts for practical water splitting technologies.
文摘Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.
基金financial support from the National Key Research and Development Program of China(2018YFA0703400)the Fundamental Research Funds for the Provincial Universities of Zhejiang(GK239909299001021)+1 种基金the Ninth China Association for Science and Technology Youth Talent Lift Project Support Plan(KYZ015324002)the Changjiang Scholars Program of Chinese Ministry of Education。
文摘Atomic surfaces are strictly required by high-performance devices of diamond.Nevertheless,diamond is the hardest material in nature,leading to the low material removal rate(MRR)and high surface roughness during machining.Noxious slurries are widely used in conventional chemical mechanical polishing(CMP),resulting in the possible pollution to the environment.Moreover,the traditional slurries normally contain more than four ingredients,causing difficulties to control the process and quality of CMP.To solve these challenges,a novel green CMP for single crystal diamond was developed,consisting of only hydrogen peroxide,diamond abrasive and Prussian blue(PB)/titania catalyst.After CMP,atomic surface is achieved with surface roughness Sa of 0.079 nm,and the MRR is 1168 nm·h^(-1).Thickness of damaged layer is merely 0.66 nm confirmed by transmission electron microscopy(TEM).X-ray photoelectron spectroscopy,electron paramagnetic resonance and TEM reveal that·OH radicals form under ultraviolet irradiation on PB/titania catalyst.The·OH radicals oxidize diamond,transforming it from monocrystalline to amorphous atomic structure,generating a soft amorphous layer.This contributes the high MRR and formation of atomic surface on diamond.The developed novel green CMP offers new insights to achieve atomic surface of diamond for potential use in their high-performance devices.
文摘The kinetics of the surface reactions of single crystal Ni3Al and polycrystal line Ni3Al0.00052 wt% B with water vapor or oxygen was investigated using XPS. Both reactions initiate at less than 1.5×10-6 Pa.s exposure. The reaction of Ni3Al does not saturote with water vapor at 0.43 Pa.s; with oxygen at 8.4×10-2 Pa.s and the oxide formed is Al2O3. The kinetics of these reactions can be used to eaplain the different ductility behavior of Ni3Al-based alloys in various environment.
基金sponsored by the National Natural Science Foundation of China under Contract 59771007a key project of the National Natural Science Foundation of China under Contract 59895157
文摘The interaction of water vapor and oxygen with TiAI-based alloy has been studied with Auger electron spectroscopy and X-ray photoelectron spectroscopy. The results indicate that both surface reactions initiate at a very short exposure (about 6×10-7 Pa·s) and the oxides Al2O3 and TiO2 form in the surface reactions. In the oxidizing reaction, the water vapor reacts firstly with Al, and then reacts with Ti after certain exposure. The surface reaction of Al with water vapor may be responsible for the environmental embrittlement at room temperature in TiAI-based alloy.
基金Funded by the National Natural Science Foundation of China(Nos.20974001,21174001,51273001,and 51403001)
文摘A simulation study was carried out by using dissipative particle dynamics(DPD) method to explore the effects of properties of coating chains, such as length, density, rigidity of polymer chains, as well as the distance between nanoparticles on bonding reaction of coating chains grafted onto nanoparticles. The results show that bonding ratios of coated chains strongly depend on the length and density of coating chains. For nanoparticles with different coating densities, the optimum chain length for bonding reaction are varied. The rigidity of coating chains exhibits vigorous effects on bonding reaction that highly depends on chain lengths. DPD simulation can be used to study the bonding reaction between coated nanoparticles, which may help experimental synthesis of nanocomposites with excellent properties.
文摘Bimetallic Pt-based catalysts have been extensively investigated to enhance the performance of direct methanol fuel cells(DMFCs) because CO, a by-product, reduces the activity of the pure Pt catalysts. Herein, we synthesized Pt-Pb hexagonal nanoplates as a model catalyst for the methanol oxidation reaction(MOR) and further controlled the Pt and Pb distributions on the surface of the nanoplates through acetic acid(HAc) treatment. As a result, we obtained Pt-Pb nanoplates and HAc-treated Pt-Pb nanoplates with homogeneous and heterogeneous distributions of the Pt-Pb alloy surfaces, respectively. We showed that the MOR activity and stability of the Pt-Pb nanoplates improved compared to those of the HAc-treated Pt-Pb nanoplates, mainly due to the enhanced CO tolerance and the modified electronic structure of Pt under the influence of the oxophilic Pb.
基金supported by the Chinese Ministry of Science and Technology(No.2008AA062503)the National Natural Science Foundation Committee of China(Nos.41421064,20637020)the China Postdoctoral Science Foundation(No.20100470166)
文摘Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography（XCT） and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional（3-D） rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy（FE-SEM） to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.
文摘Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH<span style="white-space:nowrap;">• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH<span style="white-space:nowrap;">• radicals are determined by the energies E<sub>orb</sub> of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |E<sub>orb</sub>|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.
文摘The effect of boron doping on the sensitivity to environmental embrittlement of Ni3Al-based alloys was investigated in this paper. The results show that the ductilizing effect of boron in Ni3Al is partly to suppress moisture-induced hydrogen embrittlement.The mechanism of this suppressing effect of boron relates to its severely decreasing the hydrogen diffusivity by boron segregated at the grain boundaries. The surface reaction of Fe3Al with water vapor and oxygen was experimentally confirmed by AES and XPS analysis. The kinetics of these reactions can be used to explain the different ductility behavior of aluminides in various environments.
文摘Development of reaction-tailored electrocatalysts is becoming increasingly important as energy and environment are among key issues governing our sustainable future.Electrocatalysts are inherently optimized for application towards reactions of interest in renewable energy,such as those involved in water splitting and artificial photosynthesis,owing to its energy efficiency,simple fabrication,and ease of operation.In this view,it is important to secure logical design principles for the synthesis of electrocatalysts for various reactions of interest,and also understand their catalytic mechanisms in the respective reactions for improvements in further iterations.In this review,we introduce several key methods of scanning electrochemical microscopy(SECM)in its applications towards electrocatalysis.A brief history and a handful of seminal works in the SECM field is introduced in advancing the synthetic designs of electrocatalysts and elucidation of the operating mechanism.New developments in nano-sizing of the electrodes in attempts for improved spatial resolution of SECM is also introduced,and the application of nanoelectrodes towards the investigation of formerly inaccessible single catalytic entities is shared.
基金Supported by the National Natural Science Foundation of China(No. 20173032) Ph. D. Special Research Foundation ofMinistry of Education of China(No. 20020422027).
文摘The partial potential energy surface of the I ＋ HI →IH ＋ I reaction involving the translational and vibrational motions has been constructed at the QCISD（ T ）//MP4SDQ level with the pseudo potential method that is helpful to interpreting the scattering resonance states. The lifetimes of the scattering resonance states in the title reaction obtained from the partial potential energy surface are about 90-120 fs, which agrees with the result of high-resolved threshold photodetachment spectroscopy of anion IHI^- measured by Neumark.
