The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol(SOA).However,to date,the reactivity of C2 Criege...The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol(SOA).However,to date,the reactivity of C2 Criegee intermediates(CH_(3)CHOO)in areas contaminated with acidic gas remains poorly understood.Herein,high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations are used to explore the reaction of CH_(3)CHOO and H_(2)SO_(4)both in the gas phase and at the airwater interface.In the gas phase,the addition reaction of CH_(3)CHOO with H_(2)SO_(4)to generate CH_(3)HC(OOH)OSO_(3)H(HPES)is near-barrierless,regardless of the presence of water molecules.BOMD simulations showthat the reaction at the air-water interface is even faster than that in the gas phase.Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids,ammonias,and water molecules to form stable clusters,meanwhile the oligomerization reaction of CH_(3)CHOO with HPES in the gas phase is both thermochemically and kinetically favored.Also,it is noted that the interfacial HPES−ion can attract H_(2)SO_(4),NH_(3),(COOH)_(2)and HNO_(3)for particle formation from the gas phase to the water surface.Thus,the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions,but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.展开更多
By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we rep...By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.展开更多
Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as...Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.展开更多
Detection and observation of reactive intermediates is an essential step in investigation of reaction pathways.However,most reactive intermediates are unstable and present at low concentrations;their short lifetimes m...Detection and observation of reactive intermediates is an essential step in investigation of reaction pathways.However,most reactive intermediates are unstable and present at low concentrations;their short lifetimes make them difficult to detect and characterize.Supramolecular containers offer opportunities for the stabilization and characterization of those labile species,through isolation from the media and protection inside the cavity of the host.In this review,we summarize the examples of labile reaction intermediates that are stabilized and characterized with the help of supramolecular containers.The container compounds include carcerands,deep cavitands and amide naphthotubes.We focus on unstable vip species-cyclobutadiene,benzocyclopropenone,o-benzyne,1,2,4,6-cycloheptatetraene,anti-Bredt's olefin,fluorophenoxycarbene,O-acylisoamide,and hemiaminalthat act as intermediates in certain organic reactions.展开更多
Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction int...Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst.Here,a family of n%-Co_(3)O_(4)/SiC(n=5,8,12,20)catalysts with a delicate percentage of Co^(2+)and Co^(3+)were prepared for NO_(3)RR.We found that Co^(3+)primarily acts as the active site for NO_(3)^(−)reduction to NO_(2)^(−),while Co^(2+)is responsible for the conversion of NO_(2)^(−)to NH_(3).Moreover,the conversion of these intermediates over the active sites is autonomous and separately controllable.Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia.Combining the experimental studies and density functional theory(DFT)calculations,it is discovered the pathway(^(*)NHO→^(*)NHOH→^(*)NH_(2)OH→^(*)NH_(2)→^(*)NH_(3))is more favorable due to the lowerΔG value(0.25 eV)for the rate-limiting step(^(*)NO→^(*)NHO).The NH_(3)yield rate of 8%-Co_(3)O_(4)/SiC reached 1.08 mmol/(cm^(2)h)with a Faradaic efficiency of 96.4%at−0.89 V versus the reversible hydrogen electrode(RHE),surpassing those of most reported non-noble NO_(3)RR catalysts.This strategy not only provides an efficient catalyst for NO_(3)RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites,thereby presenting a new approach to enhance the efficiency of intricate reactions.展开更多
The underlying spin-related mechanism remains unclear,and the rational manipulation of spin states is challenging due to various spin configurations under different coordination conditions.Therefore,it is urgent to st...The underlying spin-related mechanism remains unclear,and the rational manipulation of spin states is challenging due to various spin configurations under different coordination conditions.Therefore,it is urgent to study spin-dependent oxygen evolution reaction(OER)performance through a controllable method.Herein,we adopt a topochemical reaction method to synthesize a series of selenides with eg occupancies ranging from 1.67 to 1.37.The process begins with monoclinic-CoSeO_(3),featuring a distinct laminar structure and Co-O6 coordination.The topochemical reaction induces significant changes in the crystal field's intensity,leading to spin state transitions.These transitions are driven by topological changes from a Co-O-Se-O-Co to a Co-Se-Co configuration,strengthening the crystalline field and reducing eg orbital occupancy.This reconfiguration of spin states shifts the rate-determining step from desorption to adsorption for both OER and the hydrogen evolution reaction(HER),reducing the potential-determined step barrier and enhancing overall catalytic efficiency.As a result,the synthesized cobalt selenide exhibits significantly enhanced adsorption capabilities.The material demonstrates impressive overpotentials of 35 mV for HER,250 mV for OER,and 270 mV for overall water splitting,indicating superior catalytic activity and efficiency.Additionally,a negative relation between eg filling and OER catalytic performance confirms the spin-dependent nature of OER.Our findings provide crucial insights into the role of spin state transitions in catalytic performance.展开更多
Based on the different hydrophobicities of the intermediates of proteins the various conformational intermediates of the refolding of a-amylase originally denatured with 8.0 mol/L urea solution were separated with hi...Based on the different hydrophobicities of the intermediates of proteins the various conformational intermediates of the refolding of a-amylase originally denatured with 8.0 mol/L urea solution were separated with high performance hydrophobic interaction chromatography(HPHIC). Compared to the separation of the same intermediates with weak anion exchange chromatography and size-exclusion chromatography the result obtained with HPHIC is the best It would be expected that HPHIC may be a strongly potential tool to separate intermediates of some proteins which cannot be, or cannot completely be refolded by HPHIC.展开更多
This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentratio...This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentration on CB degradation were determined.The degradation effciency of CB was almost 100% with an initial CB concentration of 50 mg/L,current density 15 mA/cm2,initial pH 10,electrolyte concentration 0.1 mol/L,and temperature 25°C after 90 min of reaction.Under the same conditions,the degradation eff...展开更多
The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were i...The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).展开更多
The surface species formed in the reaction of NO and NO2 with pre-adsorbed NH 3 over a Fe-ZSM-5 catalyst(1.27 wt.%Fe,SiO2/Al2O3=25)at low temperature(140°C)were studied by in situ diffuse reflectance infrared Fou...The surface species formed in the reaction of NO and NO2 with pre-adsorbed NH 3 over a Fe-ZSM-5 catalyst(1.27 wt.%Fe,SiO2/Al2O3=25)at low temperature(140°C)were studied by in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Through using a background spectrum of NH3-saturated Fe-ZSM-5,we clearly observed the formation of common intermediates resulting from the reaction of NO2 or NO+O2 with pre-adsorbed NH3.This presents strong evidence that the oxidation of NO to form surface nitrates and nitrites is the key step for standard SCR at low temperature.In addition,the results suggest that in the SCR reaction at low temperature,the NH^4+ions absorbed on Brønsted acid sites are less active than NH3 adsorbed on Lewis acid sites related to Fe species.展开更多
A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO_(2)(denoted as Cu1Ce2)catalyst for toluene oxidation.The changes of surface and inter properties on Cu1Ce2 were investigated compari...A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO_(2)(denoted as Cu1Ce2)catalyst for toluene oxidation.The changes of surface and inter properties on Cu1Ce2 were investigated comparing with pure CeO_(2)and pure CuO.The formation of Cu-Ce interface promotes the electron transfer between Cu and Ce through Cu^(2+)+Ce^(3+)↔Cu^(+)+Ce^(4+)and leads to high redox properties and mobility of oxygen species.Thus,the Cu1Ce2 catalyst makes up the shortcoming of CeO_(2)and CuO and achieved high catalytic performance with T_(50)=234°C and T_(99)=250°C(the temperature at which 50%and 90%C_(7)H_(8)conversion is obtained,respectively)for toluene oxidation.Different reaction steps and intermediates for toluene oxidation over Cu1Ce2,CeO_(2)and CuO were detected by in situ DRIFTS,the fast benzyl species conversion and preferential transformation of benzoates into carbonates through C=C breaking over Cu1Ce2 should accelerate the reaction.展开更多
Cyanomethylene radical(HCCN)is an important intermediate in the nitrile chemistry in both the earth’s and the Titan’s atmosphere.Despite that the mechanism for the oxidation of HCCN has been already computationally ...Cyanomethylene radical(HCCN)is an important intermediate in the nitrile chemistry in both the earth’s and the Titan’s atmosphere.Despite that the mechanism for the oxidation of HCCN has been already computationally explored,the key Criegee intermediate,NCC(H)OO,remains unobserved yet.By photolyzing mixtures(1:50:1000)of either HC(N2)CN/O2/N2(266 nm)or HCCNCO/O2/N2(193 nm)at 15.0 K,the elusive carbonyl oxides NCC(H)OO,in syn-and anti-conformations,have been generated and characterized with IR spectroscopy.The spectroscopic identification is supported by ^18O-labeling experiments and the quantum chemical calculations at the BP86/6-311++G(3df,3pd)level.Upon subsequent UV-light irradiation,both conformers of NCC(H)OO further react with O2 and yield NCC(O)H and O3,whereas,the dioxirane isomer HC(O2)CN,which is lower than syn-NCC(H)OO by 23.7 kcal/mol at the CCSD(T)-F12a/aug-cc-pVTZ//BP86/6-311++G(3df,3pd)level,was not observed experimentally.展开更多
Selective functionalization of C-F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted ...Selective functionalization of C-F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed via radical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C-F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C-F bonds of CF_(3) groups via radical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications.展开更多
The catalytic oxidation of CO to CO2 by carbon monoxide dehydrogenases has been explored theoretically, and a large C-cluster model including the metal core [Ni-4Fe-4S] and surrounding residues and crystal water molec...The catalytic oxidation of CO to CO2 by carbon monoxide dehydrogenases has been explored theoretically, and a large C-cluster model including the metal core [Ni-4Fe-4S] and surrounding residues and crystal water molecules was used in density functional calculations. The key species involved in the oxidation of CO at the C-cluster, Cred1, Cred2 and Cint, have been elucidated. On the basis of computational results, the plausible enzymatic mechanism for the CO oxidation was proposed. In the catalytic reaction, the first proton abstraction from the Fe（1）-bound water leads to a precursor to accommodate CO binding and the subsequently consecutive proton transfers from the metal-bound carboxylate to the amino acid residues facilitate the release of CO2. The hydrogen-bond network around the C-cluster formed by conserved residues His93, His96, Glu299, Lys563, and four water molecules in the active domain plays an important role in proton transfer and intermediate stabilization. Predicted geometries of key species show good agreement with the reported crystal structures.展开更多
Organic active units often transform into radical intermediates during the redox processes but exhibit poor cycling stability due to the uncontrollable redox of the radicals. Herein, we report a facile and efficient s...Organic active units often transform into radical intermediates during the redox processes but exhibit poor cycling stability due to the uncontrollable redox of the radicals. Herein, we report a facile and efficient strategy to modulate the molecular orbital energies, charge transport capacities, and spin electron densities of the active units in covalent organic frameworks(COFs) via regulating the conjugated unit size to optimize the redox activity and stability of the organic radicals. COFs based on different imide conjugated units exhibit tunable discharge voltages, rate performance and cycling stabilities. Detailed characterizations and theoretical calculation reveal that imide radicals are the important active intermediates during the redox processes of these COFs. Specifically, increasing the size of the imide conjugated units could effectively delocalize the radical electrons and improve the stability of the COFs electrodes. This study offers a very effective strategy to modulate the redox chemistry of organic materials for electrochemical energy storage.展开更多
The investigation of bile pigments (bilirubin (BR), biliverdin (BV), purpurin (Pu), choletelin (Ch) etc.) by cyclic voltammetry, in-situ rapid scanning thin layer spectroelectrochemistry and ESR spectroscopy indicates...The investigation of bile pigments (bilirubin (BR), biliverdin (BV), purpurin (Pu), choletelin (Ch) etc.) by cyclic voltammetry, in-situ rapid scanning thin layer spectroelectrochemistry and ESR spectroscopy indicates that many free radical intermediates and polymers are produced during oxidation and reduction processes.展开更多
The enamines, iminium ions, and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones, but there is an extensive contro- versy about their roles. Here, the c...The enamines, iminium ions, and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones, but there is an extensive contro- versy about their roles. Here, the corresponding transition states connecting any two of the three kinds of species are located at the wB97XD/6-311＋＋G＊＊ level of theory. The calcula- tions demonstrate that the oxazolidinones are the predominant species in both the gas phase and solvents; there exists tautomeric equilibrium among these species and the equilibriums are controlled by the employed solvents and temperature in the reaction. These results demonstrate that the concentration and role of the mentioned species are controlled by the employed solvent and temperature. A new reaction pathway is presented herein for the trans- formation between iminium ions and oxazolidinones through iminium ion-water complex and oxazolidinone-water complex. The calculations demonstrate that the rate-limiting step in proline-catalyzed Mannich reaction between acetaldehyde/keteones and N-Boc imines is the formation of the C-C bond rather than the intermediates tautomerization. These calculations rationalize the available experimental observations and can be valuable in optimizing the experimental conditions of asymmetric organic-catalyzed reactions of aldehydes or ketones.展开更多
Given the high abundance of water in the atmosphere,the reaction of Criegee intermediates(CIs)with(H_(2)O)_(2) is considered to be the predominant removal pathway for CIs.However,recent experimental findings reported ...Given the high abundance of water in the atmosphere,the reaction of Criegee intermediates(CIs)with(H_(2)O)_(2) is considered to be the predominant removal pathway for CIs.However,recent experimental findings reported that the reactions of CIs with organic acids and carbonyls are faster than expected.At the same time,the interface behavior between CIs and carbonyls has not been reported so far.Here,the gas-phase and air-water interface behavior between Criegee intermediates and HCHO were explored by adopting high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations.Quantum chemical calculations evidence that the gas-phase reactions of CIs+HCHO are submerged energy or low energy barriers processes.The rate ratios speculate that the HCHO could be not only a significant tropospheric scavenger of CIs,but also an inhibitor in the oxidizing ability of CIs on SO_(x) in dry and highly polluted areas with abundant HCHO concentration.The reactions of CH_(2)OO with HCHO at the droplet’s surface follow a loop structure mechanism to produce i)SOZ(■),ii)BHMP(HOCH_(2)OOCH_(2)OH),and iii)HMHP(HOCH_(2)OOH).Considering the harsh reaction conditions between CIs and HCHO at the interface(i.e.,the two molecules must be sufficiently close to each other),the hydration of CIs is still their main atmospheric loss pathway.These results could help us get a better interpretation of the underlying CIs-aldehydes chemical processes in the global polluted urban atmospheres.展开更多
Mechanistic understanding of the active intermediates of 2,6-diaminopyridine(DAP) dinitration in the concentrated nitric-sulfuric acid system is of crucial importance for the selectivity control of target product, i.e...Mechanistic understanding of the active intermediates of 2,6-diaminopyridine(DAP) dinitration in the concentrated nitric-sulfuric acid system is of crucial importance for the selectivity control of target product, i.e., 2,6-diamino-3,5-dinitropyridine(DADNP). The active intermediates determining the product selectivity are theoretically studied. The HSO_(4)^(-)-NO_(2)^(+) complex is proposed as the dominant active nitrating intermediate for the first time, which shows low energy barrier(i.e., 10.19 kcal·mol^(-1),1 kcal = 4.186 k J) for direct dinitration of DAP to DADNP. The formed water during the reaction results in not only the formation of less active SO_(4)^(2-)-NO_(2)^(+) complex, but also the occurance of DAP sulfonation(DAP-SO_(3)H intermediate)to facilitate the formation of mononitration byproduct. Meanwhile, the accompanied thermal effects cause the generation of undesirable pyridine-NHNO_(2) intermediate, which is difficult to be rearranged to yield DADNP, inhibiting the reaction and thus giving low DAP conversion. The insights reported here elucidates the importance of thermal effects elimination and water content control, confirmed experimentally in the batch-and micro-reaction systems.展开更多
Adsorption of cyclohexene and its dehydrogenation intermediates on the nAu/Pt（100） （n = 0, 1, 2 means clean Pt, one monolayer and two layers of Au covered Pt surfaces, respectively.） has been investigated by self-...Adsorption of cyclohexene and its dehydrogenation intermediates on the nAu/Pt（100） （n = 0, 1, 2 means clean Pt, one monolayer and two layers of Au covered Pt surfaces, respectively.） has been investigated by self-consistent （GGA-PW91） density functional theory combined with periodic slab model. It is found that on the clean platinum, there are two kinds of favorable adsorption sites, i.e., hollow sites and bridge sites, and the adsorption energy at the hollow site is larger than that at the bridge site. However, on the Au/Pt and 2Au/Pt surfaces, there are three kinds of adsorption sites, and the adsorption energies are alike at both the bridge site and the top site. The magnitude order of the adsorption energies is as follows： clean Pt Au/Pt 2Au/Pt. The configurations of cyclohexene molecule have been distorted a little during the geometry optimizations. The lengths of C–M （M = Pt or Au, on the top layer of the slab） bonds are closely related to the corresponding adsorption energies.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22073059 and 22203052)the Natural Science Foundation of Shaanxi Province(No.2022JM-060)+1 种基金the Education Department of Shaanxi Provincial Government(No.23JC023)the Key Cultivation Project of Shaanxi University of Technology(No.SLG2101)。
文摘The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol(SOA).However,to date,the reactivity of C2 Criegee intermediates(CH_(3)CHOO)in areas contaminated with acidic gas remains poorly understood.Herein,high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations are used to explore the reaction of CH_(3)CHOO and H_(2)SO_(4)both in the gas phase and at the airwater interface.In the gas phase,the addition reaction of CH_(3)CHOO with H_(2)SO_(4)to generate CH_(3)HC(OOH)OSO_(3)H(HPES)is near-barrierless,regardless of the presence of water molecules.BOMD simulations showthat the reaction at the air-water interface is even faster than that in the gas phase.Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids,ammonias,and water molecules to form stable clusters,meanwhile the oligomerization reaction of CH_(3)CHOO with HPES in the gas phase is both thermochemically and kinetically favored.Also,it is noted that the interfacial HPES−ion can attract H_(2)SO_(4),NH_(3),(COOH)_(2)and HNO_(3)for particle formation from the gas phase to the water surface.Thus,the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions,but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.
基金supported by the Fundamental Research Funds for the Central Universities(22120230104).
文摘By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.
基金supported by National Natural Science Foundation of China(51876080)the Program for Taishan Scholars of Shandong Province Government,the Agricultural Innovation Program of Shandong Province(SD2019NJ015)+1 种基金the Research and Development program of Shandong Basan Graphite New Material Plant,National Natural Science Foundation of China(52076097)Key projects for inter-governmental cooperation in international science,technology and innovation(2018YFE0127500).
文摘Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.
基金supported by the National Natural Science Foundation of China(Nos.22071144 and 22101169)Shanghai Scientific and Technological Committee(No.22010500300)。
文摘Detection and observation of reactive intermediates is an essential step in investigation of reaction pathways.However,most reactive intermediates are unstable and present at low concentrations;their short lifetimes make them difficult to detect and characterize.Supramolecular containers offer opportunities for the stabilization and characterization of those labile species,through isolation from the media and protection inside the cavity of the host.In this review,we summarize the examples of labile reaction intermediates that are stabilized and characterized with the help of supramolecular containers.The container compounds include carcerands,deep cavitands and amide naphthotubes.We focus on unstable vip species-cyclobutadiene,benzocyclopropenone,o-benzyne,1,2,4,6-cycloheptatetraene,anti-Bredt's olefin,fluorophenoxycarbene,O-acylisoamide,and hemiaminalthat act as intermediates in certain organic reactions.
基金financially supported by the National Key Research and Development Program of China (2018YFA0209404)the Fundamental Research Funds for the Central Universities (DUT22LAB601)
文摘Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst.Here,a family of n%-Co_(3)O_(4)/SiC(n=5,8,12,20)catalysts with a delicate percentage of Co^(2+)and Co^(3+)were prepared for NO_(3)RR.We found that Co^(3+)primarily acts as the active site for NO_(3)^(−)reduction to NO_(2)^(−),while Co^(2+)is responsible for the conversion of NO_(2)^(−)to NH_(3).Moreover,the conversion of these intermediates over the active sites is autonomous and separately controllable.Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia.Combining the experimental studies and density functional theory(DFT)calculations,it is discovered the pathway(^(*)NHO→^(*)NHOH→^(*)NH_(2)OH→^(*)NH_(2)→^(*)NH_(3))is more favorable due to the lowerΔG value(0.25 eV)for the rate-limiting step(^(*)NO→^(*)NHO).The NH_(3)yield rate of 8%-Co_(3)O_(4)/SiC reached 1.08 mmol/(cm^(2)h)with a Faradaic efficiency of 96.4%at−0.89 V versus the reversible hydrogen electrode(RHE),surpassing those of most reported non-noble NO_(3)RR catalysts.This strategy not only provides an efficient catalyst for NO_(3)RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites,thereby presenting a new approach to enhance the efficiency of intricate reactions.
文摘The underlying spin-related mechanism remains unclear,and the rational manipulation of spin states is challenging due to various spin configurations under different coordination conditions.Therefore,it is urgent to study spin-dependent oxygen evolution reaction(OER)performance through a controllable method.Herein,we adopt a topochemical reaction method to synthesize a series of selenides with eg occupancies ranging from 1.67 to 1.37.The process begins with monoclinic-CoSeO_(3),featuring a distinct laminar structure and Co-O6 coordination.The topochemical reaction induces significant changes in the crystal field's intensity,leading to spin state transitions.These transitions are driven by topological changes from a Co-O-Se-O-Co to a Co-Se-Co configuration,strengthening the crystalline field and reducing eg orbital occupancy.This reconfiguration of spin states shifts the rate-determining step from desorption to adsorption for both OER and the hydrogen evolution reaction(HER),reducing the potential-determined step barrier and enhancing overall catalytic efficiency.As a result,the synthesized cobalt selenide exhibits significantly enhanced adsorption capabilities.The material demonstrates impressive overpotentials of 35 mV for HER,250 mV for OER,and 270 mV for overall water splitting,indicating superior catalytic activity and efficiency.Additionally,a negative relation between eg filling and OER catalytic performance confirms the spin-dependent nature of OER.Our findings provide crucial insights into the role of spin state transitions in catalytic performance.
文摘Based on the different hydrophobicities of the intermediates of proteins the various conformational intermediates of the refolding of a-amylase originally denatured with 8.0 mol/L urea solution were separated with high performance hydrophobic interaction chromatography(HPHIC). Compared to the separation of the same intermediates with weak anion exchange chromatography and size-exclusion chromatography the result obtained with HPHIC is the best It would be expected that HPHIC may be a strongly potential tool to separate intermediates of some proteins which cannot be, or cannot completely be refolded by HPHIC.
基金the Science and Technology Department of Zhejiang Province (No.2006C13120).
文摘This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentration on CB degradation were determined.The degradation effciency of CB was almost 100% with an initial CB concentration of 50 mg/L,current density 15 mA/cm2,initial pH 10,electrolyte concentration 0.1 mol/L,and temperature 25°C after 90 min of reaction.Under the same conditions,the degradation eff...
基金supported by the National Natural Science Foundation of China(No.51876080)the Strategic International Scientific and Technological Innovation Cooperation Special Funds of National Key Research and Development Program of China(No.2016YFE0204000)+3 种基金the Program for Taishan Scholars of Shandong Province Governmentthe Recruitment Program of Global Experts(Thousand Youth Talents Plan)the Natural Science Foundation of Shandong Province(ZR2017BB002)the Key Research and Development Program of Shandong Province(2018GSF116014)。
文摘The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21777174 and 21637005).
文摘The surface species formed in the reaction of NO and NO2 with pre-adsorbed NH 3 over a Fe-ZSM-5 catalyst(1.27 wt.%Fe,SiO2/Al2O3=25)at low temperature(140°C)were studied by in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Through using a background spectrum of NH3-saturated Fe-ZSM-5,we clearly observed the formation of common intermediates resulting from the reaction of NO2 or NO+O2 with pre-adsorbed NH3.This presents strong evidence that the oxidation of NO to form surface nitrates and nitrites is the key step for standard SCR at low temperature.In addition,the results suggest that in the SCR reaction at low temperature,the NH^4+ions absorbed on Brønsted acid sites are less active than NH3 adsorbed on Lewis acid sites related to Fe species.
基金financially supported by the China Postdoctoral Science Foundation(No.2018M643090)the National Natural Science Foundation of China(No.52000077)+3 种基金the National Key Research and Development Project of Research(No.2017YFC0212805)the National Natural Science Foundation of China(No.51878292)the Natural Science Foundation of Guangdong Province,China(No.2015B020236002)the China Postdoctoral Science Foundation(No.2020M682715).
文摘A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO_(2)(denoted as Cu1Ce2)catalyst for toluene oxidation.The changes of surface and inter properties on Cu1Ce2 were investigated comparing with pure CeO_(2)and pure CuO.The formation of Cu-Ce interface promotes the electron transfer between Cu and Ce through Cu^(2+)+Ce^(3+)↔Cu^(+)+Ce^(4+)and leads to high redox properties and mobility of oxygen species.Thus,the Cu1Ce2 catalyst makes up the shortcoming of CeO_(2)and CuO and achieved high catalytic performance with T_(50)=234°C and T_(99)=250°C(the temperature at which 50%and 90%C_(7)H_(8)conversion is obtained,respectively)for toluene oxidation.Different reaction steps and intermediates for toluene oxidation over Cu1Ce2,CeO_(2)and CuO were detected by in situ DRIFTS,the fast benzyl species conversion and preferential transformation of benzoates into carbonates through C=C breaking over Cu1Ce2 should accelerate the reaction.
基金supported by the National Natural Science Foundation of China (No.21673147).
文摘Cyanomethylene radical(HCCN)is an important intermediate in the nitrile chemistry in both the earth’s and the Titan’s atmosphere.Despite that the mechanism for the oxidation of HCCN has been already computationally explored,the key Criegee intermediate,NCC(H)OO,remains unobserved yet.By photolyzing mixtures(1:50:1000)of either HC(N2)CN/O2/N2(266 nm)or HCCNCO/O2/N2(193 nm)at 15.0 K,the elusive carbonyl oxides NCC(H)OO,in syn-and anti-conformations,have been generated and characterized with IR spectroscopy.The spectroscopic identification is supported by ^18O-labeling experiments and the quantum chemical calculations at the BP86/6-311++G(3df,3pd)level.Upon subsequent UV-light irradiation,both conformers of NCC(H)OO further react with O2 and yield NCC(O)H and O3,whereas,the dioxirane isomer HC(O2)CN,which is lower than syn-NCC(H)OO by 23.7 kcal/mol at the CCSD(T)-F12a/aug-cc-pVTZ//BP86/6-311++G(3df,3pd)level,was not observed experimentally.
基金National Natural Science Foundation of China (No.21971226)the Fundamental Research Funds for the Central Universities (No. WK2060000017) for financial support。
文摘Selective functionalization of C-F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed via radical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C-F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C-F bonds of CF_(3) groups via radical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications.
基金Sponsored by the National Natural Science Foundation of China (No. 20673087, 20733002, 20873105)the Ministry of Science and Technology (No. 2004CB719902)
文摘The catalytic oxidation of CO to CO2 by carbon monoxide dehydrogenases has been explored theoretically, and a large C-cluster model including the metal core [Ni-4Fe-4S] and surrounding residues and crystal water molecules was used in density functional calculations. The key species involved in the oxidation of CO at the C-cluster, Cred1, Cred2 and Cint, have been elucidated. On the basis of computational results, the plausible enzymatic mechanism for the CO oxidation was proposed. In the catalytic reaction, the first proton abstraction from the Fe（1）-bound water leads to a precursor to accommodate CO binding and the subsequently consecutive proton transfers from the metal-bound carboxylate to the amino acid residues facilitate the release of CO2. The hydrogen-bond network around the C-cluster formed by conserved residues His93, His96, Glu299, Lys563, and four water molecules in the active domain plays an important role in proton transfer and intermediate stabilization. Predicted geometries of key species show good agreement with the reported crystal structures.
基金supports from the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (No. JCYJ20200109141640095)the Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials (No. ZDSYS20200421111401738)+3 种基金the Leading Talents of Guangdong Province Program (No. 2016LJ06C536)the GuangdongHong Kong-Macao Joint Laboratory (No. 2019B121205001)the National Natural Science Foundation of China (No. 21875097)the support from the Hong Kong Research Grants Council (Project number CityU 11218420)。
文摘Organic active units often transform into radical intermediates during the redox processes but exhibit poor cycling stability due to the uncontrollable redox of the radicals. Herein, we report a facile and efficient strategy to modulate the molecular orbital energies, charge transport capacities, and spin electron densities of the active units in covalent organic frameworks(COFs) via regulating the conjugated unit size to optimize the redox activity and stability of the organic radicals. COFs based on different imide conjugated units exhibit tunable discharge voltages, rate performance and cycling stabilities. Detailed characterizations and theoretical calculation reveal that imide radicals are the important active intermediates during the redox processes of these COFs. Specifically, increasing the size of the imide conjugated units could effectively delocalize the radical electrons and improve the stability of the COFs electrodes. This study offers a very effective strategy to modulate the redox chemistry of organic materials for electrochemical energy storage.
文摘The investigation of bile pigments (bilirubin (BR), biliverdin (BV), purpurin (Pu), choletelin (Ch) etc.) by cyclic voltammetry, in-situ rapid scanning thin layer spectroelectrochemistry and ESR spectroscopy indicates that many free radical intermediates and polymers are produced during oxidation and reduction processes.
文摘The enamines, iminium ions, and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones, but there is an extensive contro- versy about their roles. Here, the corresponding transition states connecting any two of the three kinds of species are located at the wB97XD/6-311＋＋G＊＊ level of theory. The calcula- tions demonstrate that the oxazolidinones are the predominant species in both the gas phase and solvents; there exists tautomeric equilibrium among these species and the equilibriums are controlled by the employed solvents and temperature in the reaction. These results demonstrate that the concentration and role of the mentioned species are controlled by the employed solvent and temperature. A new reaction pathway is presented herein for the trans- formation between iminium ions and oxazolidinones through iminium ion-water complex and oxazolidinone-water complex. The calculations demonstrate that the rate-limiting step in proline-catalyzed Mannich reaction between acetaldehyde/keteones and N-Boc imines is the formation of the C-C bond rather than the intermediates tautomerization. These calculations rationalize the available experimental observations and can be valuable in optimizing the experimental conditions of asymmetric organic-catalyzed reactions of aldehydes or ketones.
基金support from the National Natural Science Foundation of China(Nos:22073059,42107109)the GHfund B(No:20210702)+2 种基金the Key Cultivation Project of Shaanxi University of Technology(No:SLG2101)the Funds of Graduate Innovation of Shaanxi University of Technology(No:SLGYCX2120)the State Key Laboratory of Biological Resources and Ecological Environment of Qinba Areas“City-School Co-Construction”Special Research Project(No:SXC-2110).
文摘Given the high abundance of water in the atmosphere,the reaction of Criegee intermediates(CIs)with(H_(2)O)_(2) is considered to be the predominant removal pathway for CIs.However,recent experimental findings reported that the reactions of CIs with organic acids and carbonyls are faster than expected.At the same time,the interface behavior between CIs and carbonyls has not been reported so far.Here,the gas-phase and air-water interface behavior between Criegee intermediates and HCHO were explored by adopting high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations.Quantum chemical calculations evidence that the gas-phase reactions of CIs+HCHO are submerged energy or low energy barriers processes.The rate ratios speculate that the HCHO could be not only a significant tropospheric scavenger of CIs,but also an inhibitor in the oxidizing ability of CIs on SO_(x) in dry and highly polluted areas with abundant HCHO concentration.The reactions of CH_(2)OO with HCHO at the droplet’s surface follow a loop structure mechanism to produce i)SOZ(■),ii)BHMP(HOCH_(2)OOCH_(2)OH),and iii)HMHP(HOCH_(2)OOH).Considering the harsh reaction conditions between CIs and HCHO at the interface(i.e.,the two molecules must be sufficiently close to each other),the hydration of CIs is still their main atmospheric loss pathway.These results could help us get a better interpretation of the underlying CIs-aldehydes chemical processes in the global polluted urban atmospheres.
基金financially supported by the National Natural Science Foundation of China, China (21922803, 22122807, and 22008072)the Innovation Program of Shanghai Municipal Education Commission, China+1 种基金the Program of Shanghai Academic/Technology Research Leader, China (21XD1421000)the China Postdoctoral Science Foundation, China (2020M671025 and 2019TQ0093)。
文摘Mechanistic understanding of the active intermediates of 2,6-diaminopyridine(DAP) dinitration in the concentrated nitric-sulfuric acid system is of crucial importance for the selectivity control of target product, i.e., 2,6-diamino-3,5-dinitropyridine(DADNP). The active intermediates determining the product selectivity are theoretically studied. The HSO_(4)^(-)-NO_(2)^(+) complex is proposed as the dominant active nitrating intermediate for the first time, which shows low energy barrier(i.e., 10.19 kcal·mol^(-1),1 kcal = 4.186 k J) for direct dinitration of DAP to DADNP. The formed water during the reaction results in not only the formation of less active SO_(4)^(2-)-NO_(2)^(+) complex, but also the occurance of DAP sulfonation(DAP-SO_(3)H intermediate)to facilitate the formation of mononitration byproduct. Meanwhile, the accompanied thermal effects cause the generation of undesirable pyridine-NHNO_(2) intermediate, which is difficult to be rearranged to yield DADNP, inhibiting the reaction and thus giving low DAP conversion. The insights reported here elucidates the importance of thermal effects elimination and water content control, confirmed experimentally in the batch-and micro-reaction systems.
基金supported by the National Natural Science Foundation of China (Grants No. 20273034, 20673063)supported by the NKStar HPC program
文摘Adsorption of cyclohexene and its dehydrogenation intermediates on the nAu/Pt（100） （n = 0, 1, 2 means clean Pt, one monolayer and two layers of Au covered Pt surfaces, respectively.） has been investigated by self-consistent （GGA-PW91） density functional theory combined with periodic slab model. It is found that on the clean platinum, there are two kinds of favorable adsorption sites, i.e., hollow sites and bridge sites, and the adsorption energy at the hollow site is larger than that at the bridge site. However, on the Au/Pt and 2Au/Pt surfaces, there are three kinds of adsorption sites, and the adsorption energies are alike at both the bridge site and the top site. The magnitude order of the adsorption energies is as follows： clean Pt Au/Pt 2Au/Pt. The configurations of cyclohexene molecule have been distorted a little during the geometry optimizations. The lengths of C–M （M = Pt or Au, on the top layer of the slab） bonds are closely related to the corresponding adsorption energies.
