• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    An efficient single atom catalysts Os/P3C sheet for ammonia borane dehydrogenation

    2022-07-11 03:39:50ChozhengHeQunZhngJinrongHuoLingFu
    Chinese Chemical Letters 2022年6期

    Chozheng He,Qun Zhng,Jinrong Huo,b,?,Ling Fu

    a Shaanxi Key Laboratory of Optoelectronic Functional Materials and Devices,School of Materials Science and Chemical Engineering,Institute of Environment and Energy Catalysis,Xi’an Technological University,Xi’an 710021,China

    b School of Sciences,Xi’an Technological University,Xi’an 710021,China

    c College of Resources and Environmental Engineering,Tianshui Normal University,Tianshui 741001,China

    Keywords:Ammonia borane Two-dimensional materials Dehydrogenation Single atom catalyst Microkinetic model

    ABSTRACT Ammonia borane (NH3BH3,AB) has been considered to be a promising chemical hydrogen storage material.Based on density functional theory,a series of transition metal atoms supported P3C (P3C_O) sheet is systematically investigated to screen out the most promising catalyst for dehydrogenation of AB.The results indicate that the Os/P3C and Os/P3C_O could be an efficient single atom catalyst (SACs) and the stepwise reaction pathway with free energy barrier of 2.07 and 1.54 eV respectively.Remarkably,the rate constant further quantitatively confirmed the real situation of the first step of dehydrogenation of AB on the Os/P3C and Os/P3C_O substrates.We found that kf1 at 400 K is equivalent to kf2 at 800 K,which greatly improves the temperature of the first step of AB dehydrogenation on P3C_O.We hope this work can provide a promising method for the design of catalysts for AB dehydrogenation reactions on the surface of two-dimensional materials (2D).

    In recent years,the rapid increased energy demands urged the development of alternative energy sources,which are clean and renewable [1].Hydrogen is considered as one of the best candidates to satisfy the increasing demand for an efficient and clean energy carrier because hydrogen possess higher gravimetric energy density than petroleum (120 kJ/g for hydrogenvs.44 kJ/g for petroleum) and with only water as by-product [2].However,the efficient storage [3]and production of hydrogen are still two key issues in the “hydrogen economy" [4–6];.Under the continuous exploration of predecessors,it has been demonstrated that using solid media,such as sorbent materials [7–11](activated carbon,nanotubes,carbon,metal-organic frameworks,etc.) and hydrides (metal hydrides,complex hydrides,chemical hydrides,etc.)[12–14],is the safest and most effective way to store hydrogen.Among the new hydrogen storage materials,various complex hydrides,ammonia borane (NH3BH3,AB),appears to be a suitable hydrogen source and is attracting more and more interest in the field of solid-state hydrogen storage because of its abnormally high hydrogen content of 19.6 wt% and well-behaved stability under ambient conditions.Hydrogen can be released from ABviathermolysis or catalysis in various solvents [15].Al-Kukhunet al.[16].also reported the cyclization mechanism of AB low temperature dehydrogenation.Luo and Ohno [17]reported an intramolecular stepwise dehydrogenation process catalyzed by Cp2Ti in which N-H activation precedes B-H activation.However,there are some serious drawbacks which need to be overcome in order to make it suitable for practical on-board application: (1) The relatively high dehydrogenation temperature (>100°C) and low hydrogen release rate [18,19];(2) The detailed theoretical mechanism of AB releasing hydrogen in different substrates is not well understood and further studies are required [16];(3) The by-product borazine can hinder the practical application of AB because of its toxicity [20].

    To overcome the above drawbacks and make the AB can be dehydrogenated under mild conditions.a number of approaches have been developed recently,including heating ammonia borane pyrolysis,acid catalysts [21–23],metal complex catalysts [24,25],metal particle and transition metal [11,15,26].Noted that the introduction of a catalytic amount of platinum (~2 mol%) to a solution of AB in 2-methoxyethyl ether (0.02–0.03 mol/L) results in accelerating hydrogen evolution at room temperature [27]and the RuP2[28,29]nanohybrid also can be as an efficient bifunctional catalyst for hydrolysis of AB [30].Pt-based catalysts,such as small Pt nanoparticles supported on porous chromium terephthalate (MIL-101) [31],and carbon nanotubes (CNT) [32,33],exhibit superior catalytic activity for hydrolysis of AB.Transition non-noble metals such as Cu,Ni and Co [34–36]are also widely studied to improve the use efficiency of precious metals.Unfortunately,most catalysts are relatively expensive metals [37,38]or nanoparticles (such as Rh[39],Ir [40]and Os [41]) or suffer from instability under the reaction conditions [42,43].Searching for new types of catalysts is still demanding.An alternative way is to maximize the utilization of noble metal by downsizing the size of nanoparticles even to single atoms on designed substrates [44].Due to its excellent activity,selectivity and stability,single-atom catalysts (SACs) have become eternal themes in both academia and industry [45–47].Wuet al.[48].reported that Pt SACs are supported on the surface of graphene oxide as effective catalysts for the hydrolysis of AB to hydrogen.Penget al.[49].proposed that a Rh SACs supported on oxygen-rich nitrogen-doped carbon nanosheets produced highefficiency activity for AB hydrogen production.Indeed,the wide range of metal-hydrogen bond polarization present in these compounds,combined with the interaction of the metal and the charge of the AB molecule achieves the purpose of activation [50],which offers an extremely versatile platform of efficient AB dehydrogenation catalysts.

    After Sunet al.[51]found that phosphene-graphene hybrid materials exhibit high performance,more and more graphene hybrid materials have been experimentally and theoretically demonstrated.Recently,a new P/C composite material (PC6) has been reported by Jianget al.[43,52],and this analogue of graphene is designed as a substrate with supported transition metals (TMs),which exhibited excellent catalytic activity.Similarly,Zhaoet al.[53].predicted a new buckled hexagonal P/C composite material(P3C),which have intrinsic metallicity and excellent thermal stability.Lin Long and his colleagues used density functional theory(DFT) calculations to reveal that when P3C is used as a catalyst substrate [54],SACs exhibit excellent catalytic activity for electrocatalytic reactions.Therefore,this new two-dimensional material may become a highly active catalytic substrate.

    In this paper,we evaluated the potential of TMs supported P3C(P3C_O) sheet (TM/P3C and TM/P3C_O) for AB dehydrogenation reactions.A number of TMs were considered as the supported metals to screen out promising SACs [55]for AB dehydrogenation.Then,the adsorption and activation mechanisms of AB on the SACs surface was also revealed by the analysis of charge differential density(CDD),density of states (DOS) and crystal orbital Hamilton population (COHP).And the possible reaction pathways for AB dehydrogenation are also provided [56].On the other hand,rate constants in kinetics further quantitatively confirmed the real situation of the first step of dehydrogenation of AB.Therefore,our investigations may provide a rational route to design and evaluate the efficient catalysts for AB dehydrogenation reactions.

    All the calculations are carried out with the ViennaAb InitioSimulation Package (VASP) [57]based on the density functional theory (DFT) [58].The Perdew Burke and Ernzerhof (PBE) functional within generalized gradient approximation (GGA) was used to describe the electronic exchange-correlation interaction [59,60].The projector augmented-wave (PAW) method was applied to illustrate the interaction of ion-electrons [61].The cutoff energy for the plane-wave basis is set to 400 eV.For structural elaxation and electron self-consistent calculation,the convergence criteria for energy and force are set to 10?4eV and 0.02 eV/?A,respectively.The Gamma Scheme of 2×3×1 is also employed for the geometric optimization and 6×7×1 k-points were applied to the electronic structure calculation.The Bader charge analysis [62]was used to compute the charge transfer.At the same time,the zero-point energy (ZPE) correction [63]for the total energy was adopted.Device Studio [64]program provides several functions for performing visualization,modeling,and simulation.Transition states (TS)were searched by climbing image nudged elastic band method (CINEB) [65]and further confirmed by vibrational frequency analysis.The calculation simulation process is performed on P3C surface structure,as shown in Fig.S1 (Supporting information).The lattice vectors area=10.69 ?A,b=12.35 ?A,andc=15.49 ?A.To avoid artificial interactions,a vacuum of 15 ?A was added in the Z direction[66,67].The dehydrogenation mechanisms of AB reaction catalyzed reactions all proceed on the surface [68,69].

    The 2D material P3C is obtained by calculation and prediction due to the high performance of the phosphorene-graphene hybrid material [70,71].As presented in Fig.S1a,the basic building blocks of P3C monolayers P6and P4C2rings and it owes a C2/m symmetry.We investigated the electron structure of 2D P3C by calculating the band structure and partial density of states (PDOS) (Fig.S1b).As can be seen,there are some bands crossing the Fermi level,which means it is a good conductor.2D P3C exhibits intrinsic metallic features and the high conductivities and its high thermodynamic stability was identified through Ab Initio Molecular Dynamics simulation and Phonon spectra according to the report by Zhaoet al.[72].Then,six possible adsorption sites (Bpp,Bpc,Hpp,Hpc,Tp,Tc) on the P3C monolayer are considered to confirm the energetically most favorable anchoring site for the considered TM(TMs=Fe,Co,Ni,Zr,Nb,Mo,Ru,W,Os,Zr and Pt) atoms as shown in Fig.S1a.And the most stable geometry structures of TMs/P3C sheet are shown in Fig.S2 (Supporting information).Further,the binding energy (Eb) of TM atoms on P3C monolayer is calculated to verify the stability of SACs according to the formula:Eb=EP3C-M?EP3C?EM,in which M represents different single atoms.Ebrepresents the Binding energy of M atom,EP3C-M,EP3CandEMrepresent the total energy of M adsorbed on the 2D P3C plane,2D P3C surfaces,and single atoms in bulk metals.The largeEbin Table S1(Supporting information) implies that there is a strong interaction between TMs and P3C monolayer and TM/P3C is a kind of promising and feasible SACs.

    Further,charges are redistributed due to the interactions between the supported TMs and the P3C substrate.For example,some of the TMs (Os,Pt and Ir) shown by bader charge analysis have obvious electron transfer from the P3C sheet to the TMs [73],and the other is the opposite.Interestingly,it has been reported that due to the interaction between electrons,the charged TM may activate the adsorbed molecules [74,75],which are expected to adsorb and activate AB and promote the dehydrogenation reaction of AB.Therefore,TMs/P3C tablets may provide a promising method to promote the dehydrogenation of AB under mild conditions.

    To estimate and design the most promising SACs based on P3C substrate,we have implemented a rational screening strategy,including the adsorption of AB molecules on the SACs according to the B-terminal and the N-terminal adsorption respectively.The corresponding structures are shown in Fig.S3 (Supporting information,B-terminal) and Fig.S4 (Supporting information,N-terminal).Remarkably,through structural optimization,we found that some of the AB molecules catalyzed by TMs/P3C (Fe/P3C,Ni/P3C,Zr/P3C and Mo/P3C) can only be stabilized on the substrate through Bterminal adsorption.In order to further determine the best adsorption position,we calculated the adsorption energy of the AB molecules at the B-terminal and the N-terminal.The adsorption energies of AB on the TMs/P3C were calculated by the following equation is defined as:Ead_AB=Etot?EP3C-M?EAB.WhereEtotrepresents the energy of the AB adsorbed on TMs/P3C.EP3C-MandEABare the calculated total energy of TMs/P3C and single AB,respectively.Specifically,if the adsorption energyEad_ABis a positive value,it means that the adsorption of the AB molecule on the SACs is endothermic.On the contrary,ifEad_ABis a negative value,it means that the adsorption is a spontaneous process.As shown in Fig.S5 (Supporting information),the black represents the adsorption energy of the N-terminal,and the red represents the adsorption energy of the B-terminal.The higher adsorption energy negative represents the more stable the AB molecule is adsorbed on TMs/P3C.We found that the B-terminal adsorption of the AB molecule is more stable in most cases (except for W/P3C).Therefore,all the subsequent results are developed around the Bterminal adsorption of AB (Fig.1a).And all the detailed results during the screening progress are listed in Fig.1b (pink line chart).First of all,the absorption of AB molecules is an important criterion for the subsequent AB activation and dehydrogenation reaction.Thus,the calculated adsorption energy of AB molecule on surface as following: Co/P3C (?0.922 eV)Ir/P3C (1.313 ?A)>Pt/P3C (1.308 ?A)>Co/P3C (1.286 ?A)>W/P3C(1.284 ?A)>Ni/P3C (1.282 ?A)>Fe/P3C (1.276 ?A)>Mo/P3C (1.271 ?A)>Ru/P3C (1.267 ?A)>Nb/P3C (1.253 ?A)>Zr/P3C (1.243 ?A).There is a slight increase in the bond length compared to the original BH (1.217 ?A).Especially,the B-HIIcatalyzed by the Os/P3C catalyst reached 1.335 ?A and the results further indicate that the interaction between 2D Os/P3C surface and AB molecule may promote the dissociation of H in the AB hydrolysis.Interestingly,we found that there is a certain linear relationship between the degree of activation of B-HIIand the electronegativity of TMs.As shown in Fig.S6 (Supporting information),as the electronegativity increases,the bond length of B-HIItends to elongate;this may be caused by the charge transfer and interaction strength between TMs and P3C surface.To better understand the electron distribution and transfer,we studied the CDD between Os/P3C and AB,as shown in Fig.S7 (Supporting information).The cyan and yellow areas represent electron depletion and accumulation,respectively.The adsorption of the AB molecule induces slight charge redistribution and the electron accumulation mainly occurring between the AB and the Os atom.Based on this,the Os/P3C catalyst shows a strong adsorption force for AB and B-H bond tension.Therefore,we believe that Os/P3C SAC is the most suitable candidate material for AB dehydrogenation.

    Fig.1.(a) Top and side view of Os adsorbed on P3C sheet (Os/P3C).(b) The adsorption energy of AB (Ead_AB) for different sites and corresponding bond length of B-HII (AB)on the Os/P3C.

    Fig.2.The complete free energy (ΔG) correction diagram and related structure diagrams for the dehydrogenation of AB molecules on the surface of Os/P3C.

    In the present study,we found that the reactant AB on the surface of Os/P3C can be dehydrogenated by stepwise pathway: in its first half,a B-H bond is broken to form an intermediate characterized by an H atom adsorbed at the top of C atomsviaa H-adsorbed transition state;in the second half,the adsorbed B-H bond is broken and the two adsorbed H atoms form a hydrogen moleculeviaa transition state of the H movement.More interestingly,we found that O doping on the P3C surface (Os/P3C_O) will greatly reduce the adsorption energy of AB,thereby weakening the B-H bond energy in the AB molecule,making the dehydrogenation pathway of the AB reaction easier.Selected optimized structure for the stationary points along the pathways is given in Figs.2 and 3.The relative energy values are the Gibbs free energy (ΔG) (the surface energy of 2D P3C (P3C_O) is selected as 0 level energy) except for specially mentioned,the corresponding correction data are listed in Tables S3–S6 (Supporting information).As shown in Fig.2,the structure of the stepwise reaction pathway shows that one B-H bond and NH bond in the adsorbed AB are gradually elongated,and then the H proton migrates on the surface to form a hydrogen molecule,and the remaining BH2NH2species adsorbed on the Os atom.Firstly,AB molecules are chemically adsorbed on Os/P3C,and the adsorbed B-HIIbond changes from 1.219 ?A to 1.335 ?A.The loosening of the bonds facilitates the dissociation of the first H atom in the AB dehydrogenation pathway.As shown in the structure of Fig.2,the elongated B-HIIbond undergoes a transition state TS_I (false frequency is 1328.08 cm?1),and the bond length has changed from the original 1.335 ?A to 2.993 ?A,which is almost completely broken.The energy barrier of this process is 2.07 eV,which is diffi-cult to occur at room temperature,but it is worth noting that the heat released by AB molecules adsorbed on Os/P3C is 2.14 eV,so we firmly believe that the heat released by AB adsorption can provide the heat required for self-reaction.The shed H atoms move to the C atoms on the P3C surface to form an intermediate iii with a C-H bond of 1.11 ?A.Noted that the B-HIbond has been elongated to 1.36 ?A,so there are two possible ways of evolution,namely Bterminal continuous dehydrogenation (Fig.S8 in Supporting information) and the stepwise reaction pathway (Fig.2).B-HIIfracture undergoes a transition state TSII (false frequency is 1315.22 cm?1)absorbs heat of 1.4 eV,and the energy barrier crossed is 2.61 eV.Both kinetics and thermodynamics are unfavorable.Thence,our main consideration is the stepwise reaction pathway of the N-HVIpath.

    Fig.3.The complete free energy (ΔG) correction diagram and related structure diagrams for the dehydrogenation of AB molecules on the surface of Os/P3C_O.

    In this pathway,the N-HVIbond slightly activated by the surface undergoes a transition state TS_II (false frequency is 1300.91 cm?1)with an energy barrier of 1.07 eV.Simultaneously,the HVIatom moves to the surface to form a P-H bond with a bond length of 1.44 ?A,?NH2BH2(?indicates adsorbate) gradually begins to move away from Os/P3C to form an intermediate iv,and then?NH2BH2undergoes an energy-free flattening process and leaves slightly Os/P3C surface.After that,two H atoms on the surface cross the transition state with an energy barrier of 0.94 eV to form TS_III(false frequency is 727.27 cm?1).In this process,the H atoms on the two surfaces approach each other to form a bond length of 0.94 ?A of H2molecules,while C-HIIand P-HVIare elongated to 1.43 and 2.25 ?A,respectively.The generated H2molecules are far away from the surface and accompanied by a shortening of the HH bond (0.75 ?A),which is highly consistent with the bond length of normal H2molecules (0.75 ?A).This process absorbs heat of 0.64 eV.The present results indicate that the dehydrogenation of the AB molecule on the Os/P3C surface are feasible due to the entire reaction is exothermic and has a low energy barrier.

    Fig.4.(a,b) The crystal orbital Hamiltonian population (COHP) of the B-HII bond in the AB molecule adsorbed on Os/P3C_O and Os/P3C,respectively.The bonding and anti-bonding states in ICOHP are represented by light blue and light red.(c,d) The calculated corresponding partial density of states (PDOS).

    We replaced the C atom near the Os adsorption site with an O atom to form an oxidized P3C_O substrate [76].In order to systematically evaluate the stability of the substrate,we further evaluated the stability of P3C_O through AIMD simulation [77].As shown in Fig.S9 (Supporting information),the structure maintains well at 800 K.The geometric structure is still not significantly deformed,indicating that P3C_O has high thermodynamic stability.We further carried out the MD simulation of 18 ps,the energy and temperature oscillated near the equilibrium state,and the structure of P3C_O remained good.This shows that P3C_O can exist stably at the actual reaction temperature.As shown in Fig.S7,the P3C surface doped with O stretched the B-HIIbond length to 1.457 ?A,and the N-HVI bond length to 1.053 ?A.Based on the degree of activation of the AB molecule B-HIIand N-HVIby the Os/P3C_O substrate,we studied the same dehydrogenation pathway.As shown in Fig.3,the AB molecule is adsorbed on Os/P3C_O with an adsorption energy of ?1.10 eV forms an adsorbed substance ii,undergoes a transition state TS-I (false frequency is 1371.89 cm?1),which elongates the bond length of B-HIIto 2.45 ?A,and the HIIatoms gradually transfer to the C atoms on the surface,forming an intermediate state iii with C-HIIof 1.11 ?A.After that,N-HVIbegan to be elongated and experienced TS-II (false frequency is 468.03 cm?1),and the dropped HVIcontinued to approach the surface,forming O-HVIof 2.20 ?A and P-HVIof 1.43 ?A.In the intermediate iv,the HVIon the surface undergoes TS-III (false frequency is 1084.53 cm?1)and approaches HII.Simultaneously,the?NH2BH2adsorbate starts to move away from the surface,forming a vertical structure of v with the surface of the substrate.After that,the HVIatoms on the surface pass TS-IV (false frequency is 663.99 cm?1) continues to move towards the HIIatom,forming an intermediate vi with HVI-HIIof 0.96 ?A above the P atom near Os.Finally,the formed HVI-HIIundergoes TS-V (false frequency is 61.41 cm?1) and begins to move away from the surface and the vii with HVI-HIIof 0.75 ?A is formed,and the distance between the H2molecules and the surface reaches 4.26 ?A,completely detaching from the surface.In addition,?NH2BH2can continue the dehydrogenation reaction or leave the surface to form by-products.These results indicate that the stepwise reaction pathway for AB dehydrogenation on the Os/P3C_O is energetically favorable.

    The mechanism of AB activation is also evaluated theoretically,firstly,we investigated the initial adsorption configuration and electronic structure of AB adsorbed on Os/P3C and Os/P3C_O.As shown in Table S2 (Supporting information),doping with O atoms makes the adsorption energy of AB changed from ?2.14 eV to ?1.10 eV.Interestingly,the bond length of B-HIIhas grown from 1.335 ?A to 1.417 ?A,and N-HVI(1.053 ?A).Compared with the original B-HII(1.217 ?A) and N-HVI(1.032 ?A),the AB molecule is fully activated.To figure out the nature of the interaction between supported Os atom and AB,CDD is analyzed to illustrate the interaction mechanism.It can be found from Figs.S7b and c that the charge transfer and redistribution can be observed around the AB molecule and supported Os atom,respectively.To deeply understand the activation process,ICOHP and DOS of the B-HIIbond in the first dehydrogenation reaction of AB on Os/P3C and Os/P3C_O are calculated in Figs.4a and b.The decrease of ICOHP values of B-HIIbond (from ?3.79 to ?3.62) confirms that the strength of BHIIbond of Os/P3C_O is obviously weakened.In order to deep insights into the interaction between atoms in bonding,we analyzed the interaction of the B-HIIbond by plotting PDOS.The size of the overlapping peak area of PDOS indicates the strength of the bond between atoms.It can be seen from Figs.4c and d that the integral value (0.526) of the Os/P3C surface is greater than Os/P3C_O(0.509),this result once again explains the nature of the low energy barrier of the Os/P3C_O substrate adsorption of AB in the first step of dehydrogenation reaction.

    Table 1 The relationship between the equilibrium constant (kfi) of the reaction and the reaction temperature (T), kf1 and kf2 represent the first step dehydrogenation equilibrium constant of AB on Os/P3C and Os/P3C_O,respectively.

    Rate constant [78]was performed to further verify confirmed quantitative analysis of Os/P3C and Os/P3C_O activated AB at different temperatures.The relationship between rate constants (kf i)and reaction temperature (T) is shown in the following formula[79]:

    whereviis the pre-exponential factor,andEactis the ZPE-corrected activation energy.Within harmonic transition state theory,we can calculate the pre-exponential factor (νi) of each reaction pathway using the following definition:

    whereandare the vibrational frequencies at the initial state and the vibrational frequencies at the transition state (excluding the imaginary one).

    From the above formula,we can deduce that the relationship between the first step dehydrogenation rate constant on Os/P3C and Os/P3C_O:

    whererf1andrf2are the ratio of the first step dehydrogenation rate of Os/P3C and Os/P3C_O;θABis the coverage of AB on the surface.kis the ratio of dimensionlessrf1torf2.

    Applying the same rough rule of thumb [78],the dehydrogenation energy barriers of AB in the first step of Os/P3C and Os/P3C_O are 2.07 and 0.95 eV,their reaction temperatures are 800 K and 400 K,respectively.Based on the DFT results and microkinetic model,we have calculatedkf1andkf2of 300–850 K by Eqs.1 and 2.From the data listed in Table 1,we can find that thekf1(kf2) is increased with increasing temperature due to increase it is conducive to the increase in the average kinetic energy of the molecules,the increase in the number of activated molecules and the effective collision frequency.Obviously,with the increase of temperature,the increase ofkf1andkf2and the value ofkis getting smaller and smaller,which indicates that there is a certain limit in the reaction of AB on Os/P3C and Os/P3C_O,and the sensitivity to temperature keep getting smaller.And it is worth noting that thekf1at 400 K and thekf2at 800 K are in the same order of magnitude.This not only proves the accuracy of the empirical formula [75],but also shows that the P3C surface doped with O greatly reduces the temperature of the reaction so that the reaction occurs under mild conditions.

    In our work,a DFT calculation was performed to design and evaluate the catalytic activity of TMs/P3C sheet for AB dehydrogenation.There is a strong interaction between TMs and P3C substrate,which can alter the local geometric and electronic structure and promote AB dehydrogenation reaction.According to our screening criteria,the Os/P3C can obviously activate the AB due to the electron exchange interactions.And Os/P3C (Os/P3C_O) sheet is considered as a very promising electrocatalysts for AB,which needs to suffer from a moderate Gibbs free energy barrier of 2.07 and 1.54 eV respectively.Simultaneously,the microscopic kinetic model further quantitatively confirmed the real situation of the first step of dehydrogenation of AB on the Os/P3C and Os/P3C_O substrates.We found thatkf1at 400 K is equivalent tokf2at 800 K,which greatly reduced temperature of the first step of AB dehydrogenation on Os/P3C_O.

    Declaration of competing interest

    The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

    Acknowledgments

    This study was funded by the National Natural Science Foundation of China (No.21603109),the Henan Joint Fund of the National Natural Science Foundation of China (No.U1404216),the Special Fund of Tianshui Normal University,China (No.CXJ2020-08),and the Scientific Research Program Funded by Shaanxi Provincial Education Department (No.20JK0676).Jinrong Huo was partially supported by the postgraduate research opportunities program of HZWTECH (HZWTECH-PROP).Thanks for the National Supercomputing Center in Zhengzhou.

    Supplementary materials

    Supplementary material associated with this article can be found,in the online version,at doi:10.1016/j.cclet.2022.02.055.

    av在线老鸭窝| 日日撸夜夜添| 在线观看免费高清a一片| 99热这里只有是精品在线观看| 一级爰片在线观看| 大话2 男鬼变身卡| 国产成人91sexporn| 日日爽夜夜爽网站| 午夜精品国产一区二区电影| 亚洲国产日韩一区二区| 日本色播在线视频| 免费大片18禁| 女的被弄到高潮叫床怎么办| 精品人妻熟女毛片av久久网站| 亚洲av中文av极速乱| 中文精品一卡2卡3卡4更新| 好男人视频免费观看在线| 飞空精品影院首页| 国产毛片在线视频| 亚洲熟女精品中文字幕| 国产精品女同一区二区软件| 亚洲国产欧美日韩在线播放| 女人久久www免费人成看片| 欧美日韩成人在线一区二区| 欧美日韩视频高清一区二区三区二| 97精品久久久久久久久久精品| 日韩电影二区| 久久热精品热| 免费av中文字幕在线| 免费观看无遮挡的男女| 日本欧美国产在线视频| 99热6这里只有精品| 久久久久久久久久久丰满| 国产精品99久久久久久久久| 老司机影院毛片| 高清午夜精品一区二区三区| 精品人妻偷拍中文字幕| 亚洲av成人精品一二三区| 国产精品女同一区二区软件| 国产精品熟女久久久久浪| 国产精品蜜桃在线观看| 欧美一级a爱片免费观看看| 热99久久久久精品小说推荐| 久热这里只有精品99| av有码第一页| 成人毛片a级毛片在线播放| 欧美日韩成人在线一区二区| 日韩制服骚丝袜av| 国产国拍精品亚洲av在线观看| xxxhd国产人妻xxx| 色婷婷久久久亚洲欧美| 国产深夜福利视频在线观看| 国产乱人偷精品视频| 嘟嘟电影网在线观看| 亚洲欧美色中文字幕在线| 天天影视国产精品| 一个人看视频在线观看www免费| 永久网站在线| 亚洲欧美成人综合另类久久久| √禁漫天堂资源中文www| 嫩草影院入口| 久久人人爽人人片av| 又黄又爽又刺激的免费视频.| 久久亚洲国产成人精品v| 成年人免费黄色播放视频| 波野结衣二区三区在线| 日本-黄色视频高清免费观看| 91久久精品电影网| 国产精品秋霞免费鲁丝片| 免费观看无遮挡的男女| 免费黄网站久久成人精品| 日韩中文字幕视频在线看片| 日韩亚洲欧美综合| 97在线人人人人妻| 美女脱内裤让男人舔精品视频| 日本vs欧美在线观看视频| 一区二区三区乱码不卡18| 亚洲少妇的诱惑av| 永久免费av网站大全| 国产精品三级大全| 啦啦啦啦在线视频资源| 免费av不卡在线播放| 亚洲美女视频黄频| 五月天丁香电影| 天天影视国产精品| 亚洲精品日韩在线中文字幕| 中文字幕av电影在线播放| 日本黄色片子视频| 黄色配什么色好看| 最近最新中文字幕免费大全7| 我要看黄色一级片免费的| 欧美精品高潮呻吟av久久| 久久99一区二区三区| 国产精品免费大片| 少妇熟女欧美另类| 大香蕉久久网| xxx大片免费视频| 人妻少妇偷人精品九色| 少妇的逼水好多| 超色免费av| 国产综合精华液| 青春草国产在线视频| 91精品三级在线观看| 69精品国产乱码久久久| 我要看黄色一级片免费的| 久久狼人影院| 91aial.com中文字幕在线观看| 美女xxoo啪啪120秒动态图| 婷婷色av中文字幕| 99国产综合亚洲精品| 各种免费的搞黄视频| 五月天丁香电影| 另类亚洲欧美激情| 美女主播在线视频| 婷婷色综合www| 青春草视频在线免费观看| 人成视频在线观看免费观看| 午夜免费鲁丝| 国产高清三级在线| 18在线观看网站| 青青草视频在线视频观看| 午夜精品国产一区二区电影| 边亲边吃奶的免费视频| 丰满迷人的少妇在线观看| 丝袜在线中文字幕| 久久人妻熟女aⅴ| 一级a做视频免费观看| 少妇熟女欧美另类| 国产av精品麻豆| 亚洲国产欧美在线一区| 国产精品久久久久久精品古装| 久久精品人人爽人人爽视色| 一级a做视频免费观看| 三级国产精品片| 国产在线免费精品| 久久久久久久久大av| 老司机亚洲免费影院| 久久毛片免费看一区二区三区| 亚洲色图 男人天堂 中文字幕 | 免费大片18禁| 亚洲第一av免费看| 男人操女人黄网站| 在现免费观看毛片| 九草在线视频观看| 精品久久久久久久久av| 中文字幕免费在线视频6| 美女脱内裤让男人舔精品视频| 日韩av免费高清视频| 国产亚洲一区二区精品| 欧美日韩一区二区视频在线观看视频在线| 丰满迷人的少妇在线观看| 内地一区二区视频在线| 亚洲精品视频女| 免费观看性生交大片5| 精品亚洲乱码少妇综合久久| 国产黄色免费在线视频| 国产精品久久久久久av不卡| 久久久欧美国产精品| 成人手机av| 18禁在线无遮挡免费观看视频| 国产日韩欧美在线精品| 制服诱惑二区| 简卡轻食公司| 国产男女超爽视频在线观看| 美女xxoo啪啪120秒动态图| 亚洲图色成人| 在线观看免费日韩欧美大片 | 亚洲国产精品一区二区三区在线| 久久99热这里只频精品6学生| 精品亚洲乱码少妇综合久久| 国产午夜精品久久久久久一区二区三区| 亚洲婷婷狠狠爱综合网| 少妇被粗大的猛进出69影院 | 在线观看三级黄色| 999精品在线视频| 黑丝袜美女国产一区| 2018国产大陆天天弄谢| 久久久久久久久久久丰满| 久久久久久久久久久久大奶| 亚洲精品久久午夜乱码| 免费黄频网站在线观看国产| 亚洲天堂av无毛| 国产亚洲精品久久久com| 色5月婷婷丁香| 哪个播放器可以免费观看大片| 亚洲av电影在线观看一区二区三区| a 毛片基地| 在线观看人妻少妇| www.av在线官网国产| 日本与韩国留学比较| 久久久久久久久大av| 91精品伊人久久大香线蕉| 免费黄频网站在线观看国产| 久久99蜜桃精品久久| 丰满少妇做爰视频| 午夜免费男女啪啪视频观看| 精品午夜福利在线看| 欧美丝袜亚洲另类| 久久人妻熟女aⅴ| 黄片播放在线免费| 午夜免费观看性视频| 精品国产乱码久久久久久小说| 亚洲四区av| 熟女av电影| 少妇人妻久久综合中文| 少妇熟女欧美另类| 制服丝袜香蕉在线| 91精品国产国语对白视频| 亚洲三级黄色毛片| 菩萨蛮人人尽说江南好唐韦庄| 亚洲欧美中文字幕日韩二区| 国产免费现黄频在线看| 男女国产视频网站| 精品人妻一区二区三区麻豆| 国产 一区精品| 国产精品嫩草影院av在线观看| 亚洲,欧美,日韩| 亚洲精品乱久久久久久| 99热这里只有精品一区| 看十八女毛片水多多多| 久久午夜综合久久蜜桃| 亚洲丝袜综合中文字幕| 一级毛片 在线播放| a级毛色黄片| 在线天堂最新版资源| 男女国产视频网站| 国产色婷婷99| 九九久久精品国产亚洲av麻豆| 久久人人爽人人片av| 99精国产麻豆久久婷婷| 黄色怎么调成土黄色| 亚洲三级黄色毛片| 精品一区二区免费观看| 香蕉精品网在线| 纵有疾风起免费观看全集完整版| 亚洲欧美日韩卡通动漫| 久热这里只有精品99| 精品一区二区免费观看| 中文字幕制服av| 交换朋友夫妻互换小说| 春色校园在线视频观看| 亚洲成色77777| 激情五月婷婷亚洲| 久久国产精品男人的天堂亚洲 | 亚洲色图综合在线观看| 在线播放无遮挡| 国产精品国产三级国产av玫瑰| 成人二区视频| freevideosex欧美| 亚洲欧美中文字幕日韩二区| 午夜福利在线观看免费完整高清在| av在线播放精品| 精品视频人人做人人爽| 亚洲一级一片aⅴ在线观看| 欧美成人精品欧美一级黄| 国产永久视频网站| 久久久久网色| 全区人妻精品视频| 热re99久久国产66热| 国产精品不卡视频一区二区| 欧美另类一区| 美女中出高潮动态图| 免费播放大片免费观看视频在线观看| 美女视频免费永久观看网站| 免费高清在线观看视频在线观看| 国产黄色视频一区二区在线观看| 欧美xxⅹ黑人| 亚洲欧美清纯卡通| 久久国产精品大桥未久av| 亚洲精品国产色婷婷电影| 午夜影院在线不卡| 成人国产av品久久久| 黄片无遮挡物在线观看| 色婷婷久久久亚洲欧美| 久久亚洲国产成人精品v| 久久久久久久久久久久大奶| 国产精品一区二区三区四区免费观看| 一本—道久久a久久精品蜜桃钙片| 日韩强制内射视频| 亚洲精品国产av蜜桃| 寂寞人妻少妇视频99o| 精品久久国产蜜桃| 亚洲四区av| 国产日韩欧美在线精品| 国产精品 国内视频| 精品久久国产蜜桃| 日本黄色片子视频| 色5月婷婷丁香| 大香蕉久久成人网| 亚洲av电影在线观看一区二区三区| 建设人人有责人人尽责人人享有的| 亚洲性久久影院| 国产 一区精品| 日日爽夜夜爽网站| 黑人巨大精品欧美一区二区蜜桃 | 成人午夜精彩视频在线观看| 成人毛片60女人毛片免费| 国产精品国产三级国产av玫瑰| 亚洲精品国产av成人精品| 日日啪夜夜爽| 亚洲人成77777在线视频| 欧美日韩精品成人综合77777| 9色porny在线观看| 一边摸一边做爽爽视频免费| 午夜免费男女啪啪视频观看| 伊人亚洲综合成人网| 免费av中文字幕在线| 国产精品嫩草影院av在线观看| 国产不卡av网站在线观看| 在线观看免费日韩欧美大片 | 国产爽快片一区二区三区| 黄色一级大片看看| 又大又黄又爽视频免费| 国精品久久久久久国模美| 亚洲美女搞黄在线观看| av有码第一页| 女人精品久久久久毛片| 热re99久久国产66热| 亚洲国产精品国产精品| 少妇高潮的动态图| 人人妻人人澡人人看| 国精品久久久久久国模美| 久久久久久久大尺度免费视频| 精品视频人人做人人爽| 人成视频在线观看免费观看| 国产精品一区二区在线不卡| 香蕉精品网在线| 国产在线免费精品| 亚洲国产av影院在线观看| 中文乱码字字幕精品一区二区三区| 在线观看免费视频网站a站| 国产免费一级a男人的天堂| 国产亚洲午夜精品一区二区久久| 国产老妇伦熟女老妇高清| 一级爰片在线观看| 午夜福利在线观看免费完整高清在| 亚洲国产欧美在线一区| 亚洲欧美中文字幕日韩二区| 在线观看免费视频网站a站| 只有这里有精品99| 91在线精品国自产拍蜜月| 久久久久久人妻| 精品少妇黑人巨大在线播放| 中文欧美无线码| 久久综合国产亚洲精品| 99热这里只有是精品在线观看| 亚洲精品美女久久av网站| 亚洲国产av新网站| 高清欧美精品videossex| h视频一区二区三区| 只有这里有精品99| 亚洲色图综合在线观看| 另类精品久久| 九草在线视频观看| 极品人妻少妇av视频| 99久国产av精品国产电影| 久久精品熟女亚洲av麻豆精品| 免费高清在线观看视频在线观看| 午夜免费鲁丝| 涩涩av久久男人的天堂| xxxhd国产人妻xxx| 丁香六月天网| 久久99精品国语久久久| 好男人视频免费观看在线| 欧美97在线视频| 欧美人与性动交α欧美精品济南到 | 777米奇影视久久| 国产精品久久久久久精品电影小说| 亚洲无线观看免费| 亚洲熟女精品中文字幕| 少妇猛男粗大的猛烈进出视频| 亚洲图色成人| 日本-黄色视频高清免费观看| xxx大片免费视频| 国产精品一区www在线观看| 国产一区有黄有色的免费视频| 男女啪啪激烈高潮av片| 丰满迷人的少妇在线观看| 亚洲精品456在线播放app| 国产成人精品在线电影| 亚洲精品乱久久久久久| 女性被躁到高潮视频| 午夜免费观看性视频| 日本色播在线视频| 大香蕉97超碰在线| 精品久久久噜噜| 亚洲精品久久久久久婷婷小说| 美女xxoo啪啪120秒动态图| 纯流量卡能插随身wifi吗| 99视频精品全部免费 在线| 五月玫瑰六月丁香| av女优亚洲男人天堂| 人妻一区二区av| 久久精品久久久久久噜噜老黄| 男男h啪啪无遮挡| 免费黄频网站在线观看国产| 日韩av不卡免费在线播放| 校园人妻丝袜中文字幕| 熟妇人妻不卡中文字幕| 国产av码专区亚洲av| 免费av中文字幕在线| 嘟嘟电影网在线观看| 老司机影院毛片| 国产成人精品婷婷| 一边摸一边做爽爽视频免费| 看十八女毛片水多多多| 啦啦啦在线观看免费高清www| 少妇熟女欧美另类| 大香蕉久久网| 大片电影免费在线观看免费| 另类精品久久| 寂寞人妻少妇视频99o| 午夜久久久在线观看| 久热久热在线精品观看| 男女免费视频国产| 日本爱情动作片www.在线观看| 十八禁高潮呻吟视频| 男女啪啪激烈高潮av片| 最近中文字幕高清免费大全6| 亚洲国产毛片av蜜桃av| 国产精品无大码| 亚洲成人手机| 久久毛片免费看一区二区三区| 日韩中字成人| 一本大道久久a久久精品| 国产淫语在线视频| av在线观看视频网站免费| 欧美日韩视频高清一区二区三区二| 中文字幕人妻熟人妻熟丝袜美| 超色免费av| 最后的刺客免费高清国语| 免费人成在线观看视频色| 久久99精品国语久久久| 日韩免费高清中文字幕av| kizo精华| 欧美精品一区二区免费开放| 一本久久精品| 亚洲欧美成人精品一区二区| 国产精品秋霞免费鲁丝片| 亚洲欧美日韩另类电影网站| 狠狠婷婷综合久久久久久88av| 校园人妻丝袜中文字幕| 国产成人精品一,二区| 久久精品久久久久久噜噜老黄| 最近的中文字幕免费完整| 成年人免费黄色播放视频| 亚洲精品乱久久久久久| 久久人人爽人人片av| 欧美xxⅹ黑人| 国产免费视频播放在线视频| 99久久精品一区二区三区| 日韩不卡一区二区三区视频在线| 2021少妇久久久久久久久久久| 欧美+日韩+精品| 成人国产av品久久久| 视频在线观看一区二区三区| 91精品国产国语对白视频| 成人综合一区亚洲| 男女边摸边吃奶| 中文字幕精品免费在线观看视频 | 国产伦理片在线播放av一区| 桃花免费在线播放| 麻豆精品久久久久久蜜桃| 中文字幕人妻丝袜制服| 日韩成人av中文字幕在线观看| tube8黄色片| 久久久久精品久久久久真实原创| 一边摸一边做爽爽视频免费| 最近中文字幕2019免费版| 九色成人免费人妻av| 国产日韩欧美亚洲二区| 最黄视频免费看| 在线免费观看不下载黄p国产| 99精国产麻豆久久婷婷| 观看美女的网站| 日韩欧美一区视频在线观看| 精品国产一区二区久久| 少妇熟女欧美另类| 亚洲av日韩在线播放| 91精品伊人久久大香线蕉| 亚洲欧美成人精品一区二区| 一边亲一边摸免费视频| 十八禁高潮呻吟视频| 精品久久久久久久久亚洲| 在线观看美女被高潮喷水网站| 中文字幕人妻熟人妻熟丝袜美| 国产成人精品在线电影| 国产日韩一区二区三区精品不卡 | 欧美亚洲 丝袜 人妻 在线| 久久久久人妻精品一区果冻| 天天影视国产精品| 免费播放大片免费观看视频在线观看| 99热6这里只有精品| 高清黄色对白视频在线免费看| videossex国产| 亚洲精品美女久久av网站| av天堂久久9| 日韩视频在线欧美| 久久久久精品久久久久真实原创| 韩国高清视频一区二区三区| 国产成人精品无人区| 久久97久久精品| 考比视频在线观看| 亚洲一级一片aⅴ在线观看| 午夜精品国产一区二区电影| 免费高清在线观看视频在线观看| 99久久精品国产国产毛片| 五月开心婷婷网| 免费观看a级毛片全部| 男人爽女人下面视频在线观看| 夫妻性生交免费视频一级片| 国产高清有码在线观看视频| 人妻 亚洲 视频| 777米奇影视久久| 老熟女久久久| 3wmmmm亚洲av在线观看| 妹子高潮喷水视频| 男女边摸边吃奶| 在线 av 中文字幕| 全区人妻精品视频| 少妇猛男粗大的猛烈进出视频| 午夜福利,免费看| 免费av中文字幕在线| 男人添女人高潮全过程视频| 国产精品国产三级国产av玫瑰| 国产深夜福利视频在线观看| 男人操女人黄网站| 人妻系列 视频| 国产精品国产三级专区第一集| 亚洲精品日本国产第一区| 亚洲av二区三区四区| 日本av手机在线免费观看| 国产成人一区二区在线| 国产日韩一区二区三区精品不卡 | 午夜福利网站1000一区二区三区| 2021少妇久久久久久久久久久| 国产av精品麻豆| 久久精品久久精品一区二区三区| 蜜桃在线观看..| 欧美少妇被猛烈插入视频| 免费少妇av软件| 亚州av有码| 欧美一级a爱片免费观看看| 中国三级夫妇交换| 老熟女久久久| 日韩制服骚丝袜av| 亚洲图色成人| 亚洲国产av影院在线观看| 蜜桃久久精品国产亚洲av| 成人黄色视频免费在线看| 国产日韩欧美视频二区| 亚洲av中文av极速乱| 少妇 在线观看| 欧美精品一区二区大全| 久久久久精品性色| 在线看a的网站| 中文字幕精品免费在线观看视频 | 成年人免费黄色播放视频| 在线观看美女被高潮喷水网站| 久久亚洲国产成人精品v| 男女边吃奶边做爰视频| 美女中出高潮动态图| 国产成人精品婷婷| 亚洲欧美色中文字幕在线| 日韩大片免费观看网站| 午夜福利视频在线观看免费| av免费在线看不卡| 亚洲不卡免费看| 国产欧美日韩综合在线一区二区| 久热久热在线精品观看| 一区在线观看完整版| 国产欧美日韩一区二区三区在线 | 国产精品一二三区在线看| 视频在线观看一区二区三区| 狂野欧美白嫩少妇大欣赏| 视频在线观看一区二区三区| 免费日韩欧美在线观看| 最近中文字幕2019免费版| 亚洲欧美清纯卡通| 久久人妻熟女aⅴ| 99久久精品国产国产毛片| 国产成人精品久久久久久| 亚洲av免费高清在线观看| 成人毛片60女人毛片免费| 久久久久网色| 男的添女的下面高潮视频| 97精品久久久久久久久久精品| 亚洲精品视频女| 国产亚洲一区二区精品| 哪个播放器可以免费观看大片| 18禁动态无遮挡网站| 亚洲国产av新网站| 在线观看人妻少妇| 五月玫瑰六月丁香| 久久狼人影院| 丰满乱子伦码专区| 日日摸夜夜添夜夜添av毛片| 观看美女的网站| 国产欧美亚洲国产| 人妻人人澡人人爽人人| 边亲边吃奶的免费视频| 美女国产高潮福利片在线看| 欧美精品一区二区大全| 久久久久国产精品人妻一区二区| 欧美精品人与动牲交sv欧美| 秋霞在线观看毛片| 在线观看免费日韩欧美大片 | 欧美亚洲 丝袜 人妻 在线| 欧美亚洲日本最大视频资源| 亚洲欧洲国产日韩| 精品亚洲乱码少妇综合久久| 亚州av有码| 99久久精品一区二区三区| 丰满迷人的少妇在线观看| 精品少妇黑人巨大在线播放|