The evaporation behaviors are crucial for the flame location estimation in liquid rocketengines.This work,for the first time,experimentally reports the sub-millimeter droplet evaporationcharacteristics of the corrosiv...The evaporation behaviors are crucial for the flame location estimation in liquid rocketengines.This work,for the first time,experimentally reports the sub-millimeter droplet evaporationcharacteristics of the corrosive dinitrogen tetroxide(NTO,one prevailing hypergolic oxidizer)athigh ambient pressure up to 4.5 MPa.An in-house corrosion-resistant droplet generator is usedto generate isolated flying droplets of sub-millimeter size,which are then exposed in a gas environ-ment with temperatures between 1010 K and 1210 K and pressures in the range between 2.0 MPaand 4.5 MPa,provided by an optical rapid compression machine.Parallelly,a theoretical modelconsidering both the droplet ambient convection and the NTO dissociation is developed.Resultsindicate that firstly,the present theoretical model that considers the transient droplet-ambient con-vection as well as the temperature and pressure dependent rate of dissociation shows good agree-ment with the experimentally observed droplet lifetime.In addition,the flying droplets velocityregress gradually due to momentum exchange with the ambient,which is more prominent at higherpressure.The evaporation caused droplet size reduction is consistent with the classical D^(2)-law pre-diction,in the present temperature and pressure range.Finally,higher temperature and pressureaccelerate the evaporation and an empirical correlation for the temperature and pressure dependentevaporation rate constant is proposed,which shows good agreement with experiment and simula-tion results.展开更多
Selective dinitrogen(N_(2))capture from coalbed methane(CBM)is significant in chemical industries,but it remains a challenge because of similar physicochemical properties of N_(2) and CH_(4).Herein,the adsorption of t...Selective dinitrogen(N_(2))capture from coalbed methane(CBM)is significant in chemical industries,but it remains a challenge because of similar physicochemical properties of N_(2) and CH_(4).Herein,the adsorption of them on the 2D porphyrin sheets doped with various 3d transition metal ions(marked as MPor,M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn)were comparatively investigated by using density functional theory to screen a suitable adsorbent for CBM separation.Though systematical comparison of adsorption energies of gas molecules and Gibbs free energy change the N_(2) desorption process on all MPor surfaces,FePor is confirmed to be a promising adsorbent because of its undemanding regeneration conditions and modest chemical bonding state with N_(2) molecule.Further mechanism analysis reveals that the charge transferred from lone pair of N_(2) molecule to d_(z2)orbital of Fe ion and back-donated from d_(xz)and d_(yz)orbitals of Fe ion to the unoccupiedπ*orbital of N_(2) molecule.Such hybridization of orbitals improves the selective adsorption of N_(2) from CBM.展开更多
A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and characterized.By the stoichiometric reaction of the PNN ligand li...A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and characterized.By the stoichiometric reaction of the PNN ligand lithium salt with CoCl_(2),the complex 3,(PNN)CoCl,was obtained.Then,reduction of 3 with NaBHEt3under a dinitrogen atmosphere yielded complex 5,(PNN)Co(Ⅰ)(η^(1)-N_(2)).Single-crystal X-ray analysis,IR spectrum,and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center.The reactions of 5 with carbon monoxide and 2,6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N_(2),respectively.Furthermore,these cobalt complexes,especially complex 5,demonstrated the capacity to convert dinitrogen to N(TMS)_(3)with moderate efficiency.展开更多
Reactions of gas-phase species with small molecules are being actively studied to understand the elementary steps and mechanistic details of related condensed-phase processes.Activation of the very inert N≡N triple b...Reactions of gas-phase species with small molecules are being actively studied to understand the elementary steps and mechanistic details of related condensed-phase processes.Activation of the very inert N≡N triple bond of dinitrogen molecule by isolated gas-phase species has attracted considerable interest in the past few decades.Apart from molecular adsorption and dissociative adsorption,interesting processes such as C-N coupling and degenerate ligand exchange were discovered.The present review focuses on the recent progress on adsorption,activation,and functionalization of N2 by gas-phase species(particularly metal cluster ions)using mass spectrometry,infrared photo-dissociation spectroscopy,anion photoelectron spectroscopy,and quantum chemical calculations including density functional theory and high-level ab initio calculations.Recent advances including characterization of adsorption products,dependence of clusters’reactivity on their sizes and structures,and mechanisms of N≡N weakening and splitting have been emphasized and prospects have been discussed.展开更多
The motivation to calculate this empirical model resulted from often observing—at the time disconcerting—excess dinitrogen gas (N2 concentration > background concentration) in bubble-gas emission samples, collect...The motivation to calculate this empirical model resulted from often observing—at the time disconcerting—excess dinitrogen gas (N2 concentration > background concentration) in bubble-gas emission samples, collected primarily for the purpose of carbon budget research, from Brazilian rivers and reservoirs sampled during roughly 100 field surveys lasting 4 days each on average and executed between years 2000 and 2012. We model the (serendipitously) measured dinitrogen gas above environmental concentration (N2aec) escaping in bubbles from Brazilian rivers as a function of dissolved nitrogen (N) in water. To this model, we mathematically add a pre-existing model of diffusively emitted denitrified dinitrogen (also as a function of dissolved N) from streams in the United States of America (USA). The resulting model predicts denitrified dinitrogen water-air emission from inland waters in the USA, China and Germany.展开更多
In this work, we report a theoretical exploration of the ground-state electronic structures and molecular vibrational properties of a series of binuclear zirconium complexes in the framework of density functional theo...In this work, we report a theoretical exploration of the ground-state electronic structures and molecular vibrational properties of a series of binuclear zirconium complexes in the framework of density functional theory （DFT） employing the B3LYP hybrid functional. The calculated results reveal that the electronic structure of the complex [（η^5-C5Me5）2Zr]2（μ^2, η^2, η^2-N2） is unfavorable for hydrogenation due to the exclusion of side-on dinitrogen in the LUMO＋ 1 molecular orbital as compared with the reactant 1 [（η^5-C5Me4H）2Zr]2（μ2,η^2,η^2-N2）. Besides, the structural feature of the hypothetical intermediate 1′, [（η^5C5Me4H）2Zr]2（μ2,η^2, η^2-N2）-n2, clearly implies the possibility of further hydrogenation. In addition, the distinguishing of vibrational modes of experimental intermediate 2, [（η^5-C5Me4H）2ZrH]2（μ2,η^2,η^2-N2H2）, indicates that the asymmetric stretching of Zr-N and Zr-H leads to dissociation. Moreover, the vibrational intensity of Zr-H is stronger than that of Zr-N. Therefore, it can be predicted that excess hydrogen atmosphere is necessary to ensure the dissociation of Zr-N bonds.展开更多
The title compound [Ru（bph）（PPh3）2（N2）]·（PF6）·1.5CH2Cl2 （bph = N-（benzoyl）- N＇-（picolinylidene）-hydrazine） has been prepared and characterized by X-ray diffraction analysis. It crystallizes in...The title compound [Ru（bph）（PPh3）2（N2）]·（PF6）·1.5CH2Cl2 （bph = N-（benzoyl）- N＇-（picolinylidene）-hydrazine） has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.5201（6）, b = 15.5078（6）, c = 25.0656（13） A, β= 100.257（3）°, C50.50H43Cl3F6N5OP3Ru, Mr= 1150.23, V= 5171.4（4） A3, Z = 4, F（000） = 2332, Dc = 1.477 g/cm^3 and ,μ（MoKa） = 0.615 mm^-1. The structure was refined to R = 0.0524 and wR = 0.1398 for 8060 observed reflections （I 〉 2σ（I））. The Ru-N2 and N-N bond distances are 1.919（4） and 1.133（5）A, respectively.展开更多
Dinitrogen activation under mild conditions is important but extremely challenging due to the inert nature of the N≡N triple bond evidenced by high bond dissociation energy(945 k J/mol) and large HOMOLUMO gap(10.8 e ...Dinitrogen activation under mild conditions is important but extremely challenging due to the inert nature of the N≡N triple bond evidenced by high bond dissociation energy(945 k J/mol) and large HOMOLUMO gap(10.8 e V). In comparison with largely developed transition metal systems, the reported main group species on dinitrogen activation are rare. Here, we carry out density functional theory calculations on methyleneboranes to understand the reaction mechanisms of their dinitrogen activation. It is found that the methyleneboranes without any substituent at the boron atom performs best on dinitrogen activation, which could be contributed to its small singlet-triplet gap. In addition, strong correlations are achieved on dinitrogen activation between the singlet-triplet energy gap and the reaction energies for the formation of the end-on products as well as the side-on ones. The principal interacting orbital analysis suggests that methyleneboranes can mimic transition metals to cleave the N≡N triple bond. Our findings could be helpful for experimental chemists aiming at dinitrogen activation by main group species.展开更多
Disulfide zirconium(ZrS_(2)) is a two-dimensional(2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties.However,mass production of high...Disulfide zirconium(ZrS_(2)) is a two-dimensional(2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties.However,mass production of high quality of ZrS_(2)nanosheets to realize their practical application remains a challenge.Here,we have successfully exfoliated the bulk ZrS_(2)powder with the thickness of micron into single and few-layer nanosheets through liquid-phase exfoliation in N-methylpyrrolidone(NMP) assisted via aliphatic amines as intercalators.It is found that the exfoliation yield is as high as 27.3%,which is the record value for the exfoliation of ZrS_(2)nanosheets from bulk ZrS_(2)powder,and 77.1% of ZrS_(2)nanosheets are 2-3 layers.The molecular geometric size and aliphatic amine basicity have important impact on the exfoliation.Furthermore,the ZrS_(2)nanosheets have been used as catalyst in the electrocatalytic dinitrogen reduction with the NH3yield of 57.75 μg h^(-1)mg_(cat.)^(-1),which is twice that by ZrS_(2)nanofibers reported in literature and three times that by the bulk ZrS_(2)powder.Therefore,the liquid phase exfoliation strategy reported here has great potential in mass production of ZrS_(2)nanosheets for high activity electrocatalysis.展开更多
The reaction between tripodal trisamidophosphine ligand H_(3)PN_(3)^(Ar)and V(Mes)_(3)(THF)(Mes=mesityl)yields the vanadium(Ⅲ)complex(PN_(3)^(Ar))V(1)with an open site in the axial position,which could coordinate wit...The reaction between tripodal trisamidophosphine ligand H_(3)PN_(3)^(Ar)and V(Mes)_(3)(THF)(Mes=mesityl)yields the vanadium(Ⅲ)complex(PN_(3)^(Ar))V(1)with an open site in the axial position,which could coordinate with THF,pyridine,and NH_(3)to form the corresponding adducts(2—4).The vanadium(Ⅲ)center is redox-active,as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction.Notably,a novel dinitrogen divanadium complex with a bridging N_(2)ligand,{K(THF)}_(2){[PN_(3)^(Ar)]V}_(2)(μ-N_(2))(6),was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N_(2)atmosphere.The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations.Additionally,these vanadium complexes(1,5,6)can serve as catalysts for the conversion of N_(2)into N(SiMe_(3))_(3) in the presence of reductants and Me_(3)SiCl.展开更多
In the version of this article initially published,the supporting information was incorrectly uploaded,which was a mistake not attributable to the authors.The correct version has now been replaced.
Alkyl amines are extensively utilized in various industries,such as pharmaceuticals,agrochemicals,and materials science.Traditionally,the synthesis of alkyl amines relies heavily on ammonia as the nitrogen source,whic...Alkyl amines are extensively utilized in various industries,such as pharmaceuticals,agrochemicals,and materials science.Traditionally,the synthesis of alkyl amines relies heavily on ammonia as the nitrogen source,which is generated by the energy-intensive Haber-Bosch process.This method presents considerable environmental and economic challenges owing to its high energy demand and harsh operational conditions.展开更多
Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functiona...Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.展开更多
Comprehensive Summary,The Haber-Bosch process,which is used for ammonia(NH3)synthesis,requires vast amounts of energy,accounting for approximately 1%—2%of the world's annual energy consumption.Therefore,researche...Comprehensive Summary,The Haber-Bosch process,which is used for ammonia(NH3)synthesis,requires vast amounts of energy,accounting for approximately 1%—2%of the world's annual energy consumption.Therefore,researchers in both industry and academia are interested in developing sustainable and environmentally friendly methods for synthesizing nitrogenous compounds at ambient conditions using renewable energy sources such as visible light.While several examples of thermal activation of dinitrogen molecules have been demonstrated using various transition metals and ligand frameworks,the use of light to weaken or split the strong N—N bond has been less explored.This article presents an overview of molecular complexes capable of dinitrogen photocleavage and provides mechanistic insights into the photoactivation process through experimental and theoretical studies.We believe this review will provide readers with an in-depth understanding of the current state-of-the-art and future research perspectives,particularly in the use of visible light for dinitrogen activation and transformation.展开更多
Dinitrogen(N_(2)) is the major component of the atmosphere and many factors bring about dinitrogen inertness with low reactivity. Dinitrogen activation on metal complexes and clusters under ambient condition is the lo...Dinitrogen(N_(2)) is the major component of the atmosphere and many factors bring about dinitrogen inertness with low reactivity. Dinitrogen activation on metal complexes and clusters under ambient condition is the long-standing goal in the modern chemistry. In this review,an attempt has been made to survey the mechanistic aspects of dinitrogen activation and functionalization based on different coordination binding modes of dinitrogen. Our goal is to provide a comprehensive survey of dinitrogen activation in order to guide the relevant research in the future.展开更多
Iron sites in both nitrogenase enzymes and chemical catalysts for N_(2) fixation are typically at constrained distances and angles.Herein,we report a one-electron reduction reaction realized by constrained diiron dini...Iron sites in both nitrogenase enzymes and chemical catalysts for N_(2) fixation are typically at constrained distances and angles.Herein,we report a one-electron reduction reaction realized by constrained diiron dinitrogen cores.Using the semicircular bis(β-diketiminate)ligand,a series of diiron dinitrogen complexes were synthesized,in which the N_(2) groups were allowed to bind with Fe-Ct_(N2)-Fe angles ranging from 154°to 158°(Ct_(N2)=centroid of N_(2)).One-electron reduction of complex 2a[LFe(μ-N_(2))Fe(Et_(2)O)]gave dimer product 3a[LFe(μ-N_(2))FeK]_(2)(μ-N_(2))or monomer 3b[LFe(μ-N_(2))Fe(DMAP)K].Based on superconducting quantum interference device measurements and density functional theory calculations,2a,3a,and 3b exhibited ground spin states of S=3,S=5,and S=5/2,respectively.In addition,complex 3 underwent N_(2)derivatization via a silylation pathway followed by an acidic cleavage to yield N_(2)H_(4)as the product.展开更多
Nitrogen fixation is a vital process for both nature and industry.Whereas the nitrogenase can reduce nitrogen in ambient environment in nature,the industrialized Haber-Bosch process is a high temperature and high-pres...Nitrogen fixation is a vital process for both nature and industry.Whereas the nitrogenase can reduce nitrogen in ambient environment in nature,the industrialized Haber-Bosch process is a high temperature and high-pressure process.Since the discovery of the first dinitrogen complex in 1965,many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature.However,studies of the heterogeneous process on surface are rarely addressed.Moreover,molecular scale characterization for such dinitrogen complex is lacking.Here,we present a simple model system to investigate,at the single-molecule level,the binding of dinitrogen on a surface confined iron phthalocyanine(FePc)monolayer through the combination of in-situ low-temperature scanning tunneling microscopy(LT-STM)and X-ray photoelectron spectroscopy(XPS)measurements.The iron center in FePc molecule deposited on Au(111)and highly oriented pyrolytic graphite(HOPG)surface can adsorb dinitrogen molecule at room temperature and low pressure.A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical.Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule,which greatly modifies the electronic structure of FePc.The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.展开更多
A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometr...A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometry,Mössbauer spectroscopy,and elemental analysis.The conversion relationship and the change of the spin states among the iron complexes with different valences were studied in detail.展开更多
The synthesis,characterization,and theoretical studies of titanium-μ-N_(2) complexes with di-anionic guanidinate ligands were reported as the first example of its kind.Thus,with(Me_(3)Si)_(2)N-guanidinate ligands,the...The synthesis,characterization,and theoretical studies of titanium-μ-N_(2) complexes with di-anionic guanidinate ligands were reported as the first example of its kind.Thus,with(Me_(3)Si)_(2)N-guanidinate ligands,the mono-anionic guanidinate-supported titanium-μ-N2complex 1 was obtained.Then,reduction of 1 with potassium afforded the di-anionic guanidinate-supported titanium-μ-N_(2) complex 2 via cleavage of one N–Si bond of the(Me3Si)2N substituents in 1,changing the guanidinate ligands automatically from mono-anionic to di-anionic and remarkably lengthening the bond length of theμ-N_(2).Characteristic studies and DFT calculations were performed to reveal that the di-anionic guanidinate ligands stabilized the geometry of 2 and increased the charge density on the bridging dinitrogen.展开更多
基金supported by the Natural Science Foundation of China(No.52236001)The support from Research Grants Council of Hong Kong,China(No.CityU 15218820)was also appreciated。
文摘The evaporation behaviors are crucial for the flame location estimation in liquid rocketengines.This work,for the first time,experimentally reports the sub-millimeter droplet evaporationcharacteristics of the corrosive dinitrogen tetroxide(NTO,one prevailing hypergolic oxidizer)athigh ambient pressure up to 4.5 MPa.An in-house corrosion-resistant droplet generator is usedto generate isolated flying droplets of sub-millimeter size,which are then exposed in a gas environ-ment with temperatures between 1010 K and 1210 K and pressures in the range between 2.0 MPaand 4.5 MPa,provided by an optical rapid compression machine.Parallelly,a theoretical modelconsidering both the droplet ambient convection and the NTO dissociation is developed.Resultsindicate that firstly,the present theoretical model that considers the transient droplet-ambient con-vection as well as the temperature and pressure dependent rate of dissociation shows good agree-ment with the experimentally observed droplet lifetime.In addition,the flying droplets velocityregress gradually due to momentum exchange with the ambient,which is more prominent at higherpressure.The evaporation caused droplet size reduction is consistent with the classical D^(2)-law pre-diction,in the present temperature and pressure range.Finally,higher temperature and pressureaccelerate the evaporation and an empirical correlation for the temperature and pressure dependentevaporation rate constant is proposed,which shows good agreement with experiment and simula-tion results.
基金Supported by the National Natural Science Foundation of China(Nos.52476170 and 51906232)the Natural Science Foundation of Shanxi Province of China(Nos.202303021211156,202203021212140)Project of Science and Technology Innovation Team of Shanxi Province(No.202204051002023)。
文摘Selective dinitrogen(N_(2))capture from coalbed methane(CBM)is significant in chemical industries,but it remains a challenge because of similar physicochemical properties of N_(2) and CH_(4).Herein,the adsorption of them on the 2D porphyrin sheets doped with various 3d transition metal ions(marked as MPor,M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn)were comparatively investigated by using density functional theory to screen a suitable adsorbent for CBM separation.Though systematical comparison of adsorption energies of gas molecules and Gibbs free energy change the N_(2) desorption process on all MPor surfaces,FePor is confirmed to be a promising adsorbent because of its undemanding regeneration conditions and modest chemical bonding state with N_(2) molecule.Further mechanism analysis reveals that the charge transferred from lone pair of N_(2) molecule to d_(z2)orbital of Fe ion and back-donated from d_(xz)and d_(yz)orbitals of Fe ion to the unoccupiedπ*orbital of N_(2) molecule.Such hybridization of orbitals improves the selective adsorption of N_(2) from CBM.
基金supported by the National Natural Science Foundation of China(Nos.21988101 and 22201013)Beijing Natural Science Foundation(No.2222008)supported by the High-performance Computing Platform of Peking University。
文摘A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and characterized.By the stoichiometric reaction of the PNN ligand lithium salt with CoCl_(2),the complex 3,(PNN)CoCl,was obtained.Then,reduction of 3 with NaBHEt3under a dinitrogen atmosphere yielded complex 5,(PNN)Co(Ⅰ)(η^(1)-N_(2)).Single-crystal X-ray analysis,IR spectrum,and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center.The reactions of 5 with carbon monoxide and 2,6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N_(2),respectively.Furthermore,these cobalt complexes,especially complex 5,demonstrated the capacity to convert dinitrogen to N(TMS)_(3)with moderate efficiency.
基金supported by the National Natural Science Foundation of China(No.21833011 and No.21973101)the Youth Innovation Promotion Association CAS(No.2020034)the K.C.Wong Education Foundation。
文摘Reactions of gas-phase species with small molecules are being actively studied to understand the elementary steps and mechanistic details of related condensed-phase processes.Activation of the very inert N≡N triple bond of dinitrogen molecule by isolated gas-phase species has attracted considerable interest in the past few decades.Apart from molecular adsorption and dissociative adsorption,interesting processes such as C-N coupling and degenerate ligand exchange were discovered.The present review focuses on the recent progress on adsorption,activation,and functionalization of N2 by gas-phase species(particularly metal cluster ions)using mass spectrometry,infrared photo-dissociation spectroscopy,anion photoelectron spectroscopy,and quantum chemical calculations including density functional theory and high-level ab initio calculations.Recent advances including characterization of adsorption products,dependence of clusters’reactivity on their sizes and structures,and mechanisms of N≡N weakening and splitting have been emphasized and prospects have been discussed.
文摘The motivation to calculate this empirical model resulted from often observing—at the time disconcerting—excess dinitrogen gas (N2 concentration > background concentration) in bubble-gas emission samples, collected primarily for the purpose of carbon budget research, from Brazilian rivers and reservoirs sampled during roughly 100 field surveys lasting 4 days each on average and executed between years 2000 and 2012. We model the (serendipitously) measured dinitrogen gas above environmental concentration (N2aec) escaping in bubbles from Brazilian rivers as a function of dissolved nitrogen (N) in water. To this model, we mathematically add a pre-existing model of diffusively emitted denitrified dinitrogen (also as a function of dissolved N) from streams in the United States of America (USA). The resulting model predicts denitrified dinitrogen water-air emission from inland waters in the USA, China and Germany.
基金Supported by the National Natural Science Foundation of China (No. 20573114)MOST Project of 2006DFA43020 and 2007CB815307
文摘In this work, we report a theoretical exploration of the ground-state electronic structures and molecular vibrational properties of a series of binuclear zirconium complexes in the framework of density functional theory （DFT） employing the B3LYP hybrid functional. The calculated results reveal that the electronic structure of the complex [（η^5-C5Me5）2Zr]2（μ^2, η^2, η^2-N2） is unfavorable for hydrogenation due to the exclusion of side-on dinitrogen in the LUMO＋ 1 molecular orbital as compared with the reactant 1 [（η^5-C5Me4H）2Zr]2（μ2,η^2,η^2-N2）. Besides, the structural feature of the hypothetical intermediate 1′, [（η^5C5Me4H）2Zr]2（μ2,η^2, η^2-N2）-n2, clearly implies the possibility of further hydrogenation. In addition, the distinguishing of vibrational modes of experimental intermediate 2, [（η^5-C5Me4H）2ZrH]2（μ2,η^2,η^2-N2H2）, indicates that the asymmetric stretching of Zr-N and Zr-H leads to dissociation. Moreover, the vibrational intensity of Zr-H is stronger than that of Zr-N. Therefore, it can be predicted that excess hydrogen atmosphere is necessary to ensure the dissociation of Zr-N bonds.
文摘The title compound [Ru（bph）（PPh3）2（N2）]·（PF6）·1.5CH2Cl2 （bph = N-（benzoyl）- N＇-（picolinylidene）-hydrazine） has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.5201（6）, b = 15.5078（6）, c = 25.0656（13） A, β= 100.257（3）°, C50.50H43Cl3F6N5OP3Ru, Mr= 1150.23, V= 5171.4（4） A3, Z = 4, F（000） = 2332, Dc = 1.477 g/cm^3 and ,μ（MoKa） = 0.615 mm^-1. The structure was refined to R = 0.0524 and wR = 0.1398 for 8060 observed reflections （I 〉 2σ（I））. The Ru-N2 and N-N bond distances are 1.919（4） and 1.133（5）A, respectively.
基金Financial support by the National Science Foundation of China (No. 22073079)the Top-Notch Young Talents Program of China is gratefully acknowledged。
文摘Dinitrogen activation under mild conditions is important but extremely challenging due to the inert nature of the N≡N triple bond evidenced by high bond dissociation energy(945 k J/mol) and large HOMOLUMO gap(10.8 e V). In comparison with largely developed transition metal systems, the reported main group species on dinitrogen activation are rare. Here, we carry out density functional theory calculations on methyleneboranes to understand the reaction mechanisms of their dinitrogen activation. It is found that the methyleneboranes without any substituent at the boron atom performs best on dinitrogen activation, which could be contributed to its small singlet-triplet gap. In addition, strong correlations are achieved on dinitrogen activation between the singlet-triplet energy gap and the reaction energies for the formation of the end-on products as well as the side-on ones. The principal interacting orbital analysis suggests that methyleneboranes can mimic transition metals to cleave the N≡N triple bond. Our findings could be helpful for experimental chemists aiming at dinitrogen activation by main group species.
基金the financial supports from the National Natural Science Foundation of China (No.U1704251 and 21733011)the National Key Research and Development Program of China (2017YFA0403101)+1 种基金Natural Science Foundation of Henan province (No.202300410220)the 111 Project (No.D17007)。
文摘Disulfide zirconium(ZrS_(2)) is a two-dimensional(2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties.However,mass production of high quality of ZrS_(2)nanosheets to realize their practical application remains a challenge.Here,we have successfully exfoliated the bulk ZrS_(2)powder with the thickness of micron into single and few-layer nanosheets through liquid-phase exfoliation in N-methylpyrrolidone(NMP) assisted via aliphatic amines as intercalators.It is found that the exfoliation yield is as high as 27.3%,which is the record value for the exfoliation of ZrS_(2)nanosheets from bulk ZrS_(2)powder,and 77.1% of ZrS_(2)nanosheets are 2-3 layers.The molecular geometric size and aliphatic amine basicity have important impact on the exfoliation.Furthermore,the ZrS_(2)nanosheets have been used as catalyst in the electrocatalytic dinitrogen reduction with the NH3yield of 57.75 μg h^(-1)mg_(cat.)^(-1),which is twice that by ZrS_(2)nanofibers reported in literature and three times that by the bulk ZrS_(2)powder.Therefore,the liquid phase exfoliation strategy reported here has great potential in mass production of ZrS_(2)nanosheets for high activity electrocatalysis.
基金supported by the National Natural Science Foundation of China(21988101 for Z.-J.S.,22201044 for D.-D.Z.,22071029 for F.L.)Fundamental Research Funds for the Central Universities(20720220010).
文摘The reaction between tripodal trisamidophosphine ligand H_(3)PN_(3)^(Ar)and V(Mes)_(3)(THF)(Mes=mesityl)yields the vanadium(Ⅲ)complex(PN_(3)^(Ar))V(1)with an open site in the axial position,which could coordinate with THF,pyridine,and NH_(3)to form the corresponding adducts(2—4).The vanadium(Ⅲ)center is redox-active,as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction.Notably,a novel dinitrogen divanadium complex with a bridging N_(2)ligand,{K(THF)}_(2){[PN_(3)^(Ar)]V}_(2)(μ-N_(2))(6),was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N_(2)atmosphere.The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations.Additionally,these vanadium complexes(1,5,6)can serve as catalysts for the conversion of N_(2)into N(SiMe_(3))_(3) in the presence of reductants and Me_(3)SiCl.
文摘In the version of this article initially published,the supporting information was incorrectly uploaded,which was a mistake not attributable to the authors.The correct version has now been replaced.
基金support from the National Key R&D Program of China 2023YFB3508000the Project of Talent Cultivation for Carbon Peak and Carbon Neutrality of the University of Chinese Academy of Sciences+2 种基金supported by the Major Science and Technology Projects in Gansu Province 22ZD6GA003(L.H.)the National Natural Science Foundation of U22B20137,22302214(L.H.)the National Key R&D Program of China 2022YFA1504602(L.H.).
文摘Alkyl amines are extensively utilized in various industries,such as pharmaceuticals,agrochemicals,and materials science.Traditionally,the synthesis of alkyl amines relies heavily on ammonia as the nitrogen source,which is generated by the energy-intensive Haber-Bosch process.This method presents considerable environmental and economic challenges owing to its high energy demand and harsh operational conditions.
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101)M.Z.acknowledges China Postdoctoral Science Foundation(no.2019M650294)+1 种基金L.Z.acknowledges the financial support from NSFC(nos.21973044 and 21703099)Natural Science Foundation of Jiangsu Province for Youth(no.BK20170964)。
文摘Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.
基金the National Natural Science Foundation of China(Nos.21988101 and 22201013)Beijing Natural Science Foundation(No.2222008).
文摘Comprehensive Summary,The Haber-Bosch process,which is used for ammonia(NH3)synthesis,requires vast amounts of energy,accounting for approximately 1%—2%of the world's annual energy consumption.Therefore,researchers in both industry and academia are interested in developing sustainable and environmentally friendly methods for synthesizing nitrogenous compounds at ambient conditions using renewable energy sources such as visible light.While several examples of thermal activation of dinitrogen molecules have been demonstrated using various transition metals and ligand frameworks,the use of light to weaken or split the strong N—N bond has been less explored.This article presents an overview of molecular complexes capable of dinitrogen photocleavage and provides mechanistic insights into the photoactivation process through experimental and theoretical studies.We believe this review will provide readers with an in-depth understanding of the current state-of-the-art and future research perspectives,particularly in the use of visible light for dinitrogen activation and transformation.
基金National Natural Science Foundation of China(21902182,22033005 and 22038002)Fundamental Research Funds for the Central Universities(2022YQHH01)The support of Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)is also acknowledged.
文摘Dinitrogen(N_(2)) is the major component of the atmosphere and many factors bring about dinitrogen inertness with low reactivity. Dinitrogen activation on metal complexes and clusters under ambient condition is the long-standing goal in the modern chemistry. In this review,an attempt has been made to survey the mechanistic aspects of dinitrogen activation and functionalization based on different coordination binding modes of dinitrogen. Our goal is to provide a comprehensive survey of dinitrogen activation in order to guide the relevant research in the future.
基金supported by National Natural Science Foundation of China(grant nos.21988101,22201013,92161204)China Postdoctoral Science Foundation(grant no.2020M670016)Beijing Natural Science Foundation(grant no.2222008).
文摘Iron sites in both nitrogenase enzymes and chemical catalysts for N_(2) fixation are typically at constrained distances and angles.Herein,we report a one-electron reduction reaction realized by constrained diiron dinitrogen cores.Using the semicircular bis(β-diketiminate)ligand,a series of diiron dinitrogen complexes were synthesized,in which the N_(2) groups were allowed to bind with Fe-Ct_(N2)-Fe angles ranging from 154°to 158°(Ct_(N2)=centroid of N_(2)).One-electron reduction of complex 2a[LFe(μ-N_(2))Fe(Et_(2)O)]gave dimer product 3a[LFe(μ-N_(2))FeK]_(2)(μ-N_(2))or monomer 3b[LFe(μ-N_(2))Fe(DMAP)K].Based on superconducting quantum interference device measurements and density functional theory calculations,2a,3a,and 3b exhibited ground spin states of S=3,S=5,and S=5/2,respectively.In addition,complex 3 underwent N_(2)derivatization via a silylation pathway followed by an acidic cleavage to yield N_(2)H_(4)as the product.
基金Authors acknowledge the financial support from Singapore National Research Foundation under NRF2017NRF-NSFC001-007Singapore MOE grant of MOE2019-T2-1-002 and NUS Flagship Green Energy Program.
文摘Nitrogen fixation is a vital process for both nature and industry.Whereas the nitrogenase can reduce nitrogen in ambient environment in nature,the industrialized Haber-Bosch process is a high temperature and high-pressure process.Since the discovery of the first dinitrogen complex in 1965,many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature.However,studies of the heterogeneous process on surface are rarely addressed.Moreover,molecular scale characterization for such dinitrogen complex is lacking.Here,we present a simple model system to investigate,at the single-molecule level,the binding of dinitrogen on a surface confined iron phthalocyanine(FePc)monolayer through the combination of in-situ low-temperature scanning tunneling microscopy(LT-STM)and X-ray photoelectron spectroscopy(XPS)measurements.The iron center in FePc molecule deposited on Au(111)and highly oriented pyrolytic graphite(HOPG)surface can adsorb dinitrogen molecule at room temperature and low pressure.A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical.Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule,which greatly modifies the electronic structure of FePc.The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101).
文摘A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometry,Mössbauer spectroscopy,and elemental analysis.The conversion relationship and the change of the spin states among the iron complexes with different valences were studied in detail.
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air, the National Natural Science Foundation of China (21988101)supported by the High-performance Computing Platform of Peking University
文摘The synthesis,characterization,and theoretical studies of titanium-μ-N_(2) complexes with di-anionic guanidinate ligands were reported as the first example of its kind.Thus,with(Me_(3)Si)_(2)N-guanidinate ligands,the mono-anionic guanidinate-supported titanium-μ-N2complex 1 was obtained.Then,reduction of 1 with potassium afforded the di-anionic guanidinate-supported titanium-μ-N_(2) complex 2 via cleavage of one N–Si bond of the(Me3Si)2N substituents in 1,changing the guanidinate ligands automatically from mono-anionic to di-anionic and remarkably lengthening the bond length of theμ-N_(2).Characteristic studies and DFT calculations were performed to reveal that the di-anionic guanidinate ligands stabilized the geometry of 2 and increased the charge density on the bridging dinitrogen.
