Complexes of HNO3 and NO3 - with NO2 and N2O4, and their potential role in atmospheric HONO formation

Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO(3)).(NO(2)), (HNO(3)).(N(2)O(4)), (NO(3)(-)).(NO(2)), and (NO(3)(-)).(N(2)O(4)). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO(3)(-)).(N(2)O(4)) possessing binding energy of almost -14 kcal mol(-1). Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm(-1) that are attributed to NO(2) complexed to NO(3)(-) and HNO(3), respectively. The electronic states of (HNO(3)).(N(2)O(4)) and (NO(3)(-)).(N(2)O(4)) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO(3)(-)).(N(2)O(4)) was obtained from UV/vis absorption spectra of N(2)O(4) in concentrated HNO(3), which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N(2)O(4) dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO(3)).(NO(2)) and (HNO(3)).(N(2)O(4)) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.     

CH3与NO2的反应

The elementary reaction of the CH3 radical with NO2 was investigated by time-resolved FTIR spectroscopy and quantum chemical calculations. The CH3 radical was produced by laser photolysis of CH3Br or CH3I at 248 nm. Vibrationally excited products OH, HNO and CO2 were observed by the time-resolved spectroscopy for the first time. The formation of another product NO was also verified. According to these observations, the product channels leading to CH3O+NO, CH2NO+OH and HNO+H2CO were identified. The channel of CH3O+NO was the major one. The reaction mechanisms of the above channels were studied by quantum chemical calculations at CCSD(T)/6-311++G(df,p)//MP2/6-311G(d,p) level. The calculated results fit with the experimental observations well.     

Heterogeneous reaction of suspended phosmet particles with NO3 radicals

As an organophosphorous insecticide, phosmet is widely used for plant protection as well as against the ectoparasites on productive livestock. It emits into the atmosphere in both gas and particulate phases via spray drift from treatments and postapplication emissions, but its degradation in the atmosphere is not well-known up to now. In this study, the heterogeneous reaction of phosmet absorbed on the azelaic acid particles with NO(3) radicals is investigated in real-time using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Two primary products and their nitro-substituted derivates are observed. The apparent reaction rate of phosmet particles with NO(3) radicals is also obtained by a relative rate method with isoprene and 1,4-cyclohexadiene as the reference compounds. The concentrations of the reference substance and phosmet particles are synchronously detected with an atmospheric gas analysis mass spectrometer and the VUV-ATOFMS. Under the experimental conditions, the average apparent reaction rate obtained is (1.92 ± 0.09) × 10(-12) cm(3) molecule(-1) s(-1), and the corresponding atmospheric lifetime toward NO(3) radicals is roughly estimated to be ~0.3 h.     

New members of a class of dinitrosyliron complexes (DNICs): interconversion and spectroscopic discrimination of the anionic {Fe(NO)2}9 [(NO)2Fe(C3H3N2)2]- and [(NO)2Fe(C3H3N2)(SR)]- (C3H3N2 = deprotonated imidazole; R = tBu, Et, Ph)

The anionic {Fe(NO)2}(9) DNIC[(NO)2Fe(C3H3N2)2](-) (2) (C3H3N2 = deprotonated imidazole) containing the deprotonated imidazole-coordinated ligands and DNICs [(NO)2Fe(C3H3N2)(SR)](-) (R = (t)Bu(3), Et(4), Ph(5)) containing the mixed deprotonated imidazole-thiolate coordinated ligands, respectively, were synthesized by thiol protonation or thiolate(s) ligand-exchange reaction. The anionic {Fe(NO)2}(9) DNICs 2- 5 were characterized by IR, UV-vis, EPR, and single-crystal X-ray diffraction. The facile transformation among the anionic {Fe(NO)2}(9) DNICs 2- 5 and [(NO)2Fe(S(t)Bu)2](-)/[(NO)2Fe(SEt)2](-)/[(NO)2Fe(SPh)2](-) was demonstrated in this systematic study. Of importance, the distinct electron-donating ability of thiolates serve to regulate the stability of the anionic {Fe(NO)2}(9) DNICs and the ligand-substitution reactions of DNICs. At 298 K, DNIC 2 exhibits the nine-line EPR signal with g = 2.027 (aN(NO) = 2.20 and aN(Im-H) = 3.15 G; Im-H = deprotonated imidazole) and DNIC 3 displays the nine-line signals with g = 2.027 (aN(NO) = 2.35 and aN(Im-H) = 4.10 G). Interestingly, the EPR spectrum of complex 4 exhibits a well-resolved 11-line pattern with g = 2.027 (aN(NO) = 2.50, aN(Im-H) = 4.10 G, and aH = 1.55 G) at 298 K. The EPR spectra (the pattern of hyperfine splitting) in combination with IR nu NO spectra (DeltanuNO = the separation of NO stretching frequencies, DeltanuNO = approximately 62 cm (-1) for 2 vs approximately 50 cm(-1) for 3- 5 vs approximately 43 cm(-1) for [(NO)2Fe(S(t)Bu)2](-)/[(NO)2Fe(SEt)2](-)/[(NO)2Fe(SPh)2](-)) may serve as an efficient tool for the discrimination of the existence of the anionic {Fe(NO)2}(9) DNICs containing the different ligations [N,N]/[N,S]/[S,S].     

Dynamics of proton recombination with NO3- anion in water clusters

Recombination events of a proton with NO3- at (H2O)8 clusters are studied by molecular dynamics, using "on-the-fly" reliable ab initio MP2 potentials. The main findings are: (1) the lifetime of the ions is less than 1.2 picoseconds; (2) the recombination step invariably involves H3O+, not H5O2+; and (3) an essentially unique transition-state structure of H3O+/NO3- for recombination is found in all cases. Proton migration involves both H3O+ and H5O2+ species: Grotthuss and other mechanisms contribute.     

The reaction of Li[Al(OR)4] R = OC(CF3)2Ph, OC(CF3)3 with NO/NO2 giving NO[Al(OR)4], Li[NO3] and N2O. The synthesis of NO[Al(OR)4] from Li[Al(OR)4] and NO[SbF6] in sulfur dioxide solution

NO[Al(OC(CF(3))(2)Ph)(4)] 1 and NO[Al(OC(CF(3))(3))(4)] 2 were obtained by the metathesis reaction of NO[SbF(6)] and the corresponding Li[Al(OR)(4)] salts in liquid sulfur dioxide solution in ca 40% (1) and 85% (2) isolated yield. 1 and 2, as well as Li[NO(3)] and N(2)O, were also given by the reaction of an excess of mixture of (90 mol%) NO, (10 mol%) NO(2) with Li[Al(OR)(4)] followed by extraction with SO(2). The unfavourable disproportionation reaction of 2NO(2)(g) to [NO](+)(g) and [NO(3)](-)(g)[DeltaH degrees = +616.2 kJ mol(-1)] is more than compensated by the disproportionation energy of 3NO(g) to N(2)O(g) and NO(2)(g)[DeltaH degrees =-155.4 kJ mol(-1)] and the lattice energy of Li[NO(3)](s)[U(POT)= 862 kJ mol(-1)]. Evidence is presented that the reaction proceeds via a complex of [Li](+) with NO, NO(2)(or their dimers) and N(2)O. NO(2) and Li[Al(OC(CF(3))(3))(4)] gave [NO(3)(NO)(3)][Al(OC(CF(3))(3))(4)](2), NO[Al(OC(CF(3))(3))(4)] and (NO(2))[Al(OC(CF(3))(3))(4)] products. The aluminium complex [Li[AlF(OC(CF(3))(2)Ph)(3)]](2) 3 was prepared by the thermal decomposition of Li[Al(OC(CF(3))(2)Ph)(4)]. Compounds 1 and 3 were characterized by single crystal X-ray structural analyses, 1-3 by elemental analyses, NMR, IR, Raman and mass spectra. Solid 1 contains [Al(OC(CF(3))(2)Ph)(4)](-) and [NO](+) weakly linked via donor acceptor interactions, while in the SO(2) solution there is an equilibrium between the associated [NO](+)[Al(OC(CF(3))(2)Ph)(4)](-) and separated solvated ions. Solid 2 contains essentially ionic [NO](+) and [Al(OC(CF(3))(3))(4)](-). Complex 3 consists of two [Li[AlF(OC(CF(3))(2)Ph)(3)]] units linked via fluorine lithium contacts. Compound 1 is unstable in the SO(2) solution and decomposes to yield [AlF(OC(CF(3))(2)Ph)(3)](-), [(PhC(CF(3))(2)O)(3)Al(mu-F)Al(OC(CF(3))(2)Ph)(3)](-) anions as well as (NO)C(6)H(4)C(CF(3))(2)OH, while compound 2 is stable in liquid SO(2). The [small nu](NO(+)) in 1 and [NO](+)(toluene)[SbCl(6)] are similar, implying similar basicities of [Al(OC(CF(3))(2)Ph)(4)](-) and toluene.     

Reaction of the radical pair NO2* and CO3*- with 2-[6-(4'-amino)phenoxy-3H-xanthen-3-on-9-yl]benzoic acid (APF)

The fluorogenic indicator 2-[6-(4'-amino)phenoxy-3H-xanthen-3-on-9-yl]benzoic acid (APF) is used widely to detect and measure reactive nitrogen and oxygen species such as peroxynitrite, ONOO-, both in vivo and in vitro. We present in this work the results of a combined computational and experimental study to provide insights into the mechanism of the reaction of APF with the radical products of ONOO- reaction with CO2, namely NO2* and CO3*-. The experimental study on the inhibition of APF oxidation by HCO3- suggests that a direct reaction of APF with nitrosoperoxycarbonate, ONOOCO2-, is unlikely. The mechanism of APF action on NO2* and CO3*- was investigated using gas-phase and solvent modeled calculations at the MPW1K/6-311+G(d)//MPW1K/6-31G(d) level of theory. Our computational results suggest that two-electron oxidation of APF takes place in two rapid one-electron oxidation steps, the first being a proton-coupled electron transfer (PCET) between APF and NO2*, followed by addition of CO3*- and subsequent decomposition of the adduct to yield fluorescein.     

Reactive uptake of NO3, N2O5, NO2, HNO3, and O3 on three types of polycyclic aromatic hydrocarbon surfaces

We investigated the reactive uptake of NO3, N2O5, NO2, HNO3, and O3 on three types of solid polycyclic aromatic hydrocarbons (PAHs) using a coated wall flow tube reactor coupled to a chemical ionization mass spectrometer. The PAH surfaces studied were the 4-ring systems pyrene, benz[a]anthracene, and fluoranthene. Reaction of NO3 radicals with all three PAHs was observed to be very fast with the reactive uptake coefficient, gamma, ranging from 0.059 (+0.11/-0.049) for benz[a]anthracene at 273 K to 0.79 (+0.21/-0.67) for pyrene at room temperature. In contrast to the NO3 reactions, reactions of the different PAHs with the other gas-phase species (N2O5, NO2, HNO3, and O3) were at or below the detection limit (gamma 相似文献   

CF3O2自由基和NO反应机理的理论研究

用密度泛函理论(DFT)的B3LYP方法, 分别在6-31G、6-311G、6-311+G(d)基组水平上研究了CF3O2自由基和NO反应机理. 研究结果表明, CF3O2自由基和NO反应存在三条可行的反应通道, 优化得到了相应的中间体和过渡态. 从活化能看, 通道CH3O2+NO→IM1→TS1→IM2→TS2→CF3O+ONO的活化能最低, 仅为70.86 kJ•mol-1, 是主要反应通道, 主要产物是CF3O和NO2. 而通道CH3O2+NO→IM1→TS3→CF3ONO2和CH3O2+NO→TS4→IM3→TS5→IM4→TS6→CF3O+NOO的活化能较高, 故该反应难以进行.     

Theoretical study on the reaction mechanism of (CH3)3CO(.) radical with NO

The reaction mechanism of (CH3)3CO(.) radical with NO is theoretically investigated at the B3LYP/6-31G* level. The results show that the reaction is multi-channel in the single state and triplet state. The potential energy surfaces of reaction paths in the single state are lower than that in the triple state. The balance reaction: (CH3)3CONO←→ (CH3)3CO(.)+NO, whose potential energy surface is the lowest in all the reaction paths, makes the probability of measuring (CH3)3CO(.) radical increase. So NO may be considered as a stabilizing reagent for the (CH3)3CO(.)radical.     

离子色谱法测定乌龙茶叶中的F-、NO2-、NO3-

应用离子色谱法测定乌龙茶叶中的F~-、NO_2~-和NO_3~-。测得3种样品中F~-、NO_2~-和NO_3~-的含量分别为1.19～1.75、0.000～0.020和0.024～0.058 mg/g,加标回收率分别为94.9％、96.7％和93.4％。     

Heterogeneous oxidation kinetics of organic biomass burning aerosol surrogates by O3, NO2, N2O5, and NO3

The reactive uptake coefficients (γ) of O(3), NO(2), N(2)O(5), and NO(3) by levoglucosan, abietic acid, nitroguaiacol, and an atmospherically relevant mixture of those species serving as surrogates for biomass burning aerosol have been determined employing a chemical ionization mass spectrometer coupled to a rotating-wall flow-tube reactor. γ of O(3), NO(2), N(2)O(5), and NO(3) in the presence of O(2) are in the range of 1-8 × 10(-5), <10(-6)-5 × 10(-5), 4-6 × 10(-5), and 1-26 × 10(-3), respectively, for the investigated organic substrates. Within experimental uncertainties the uptake of NO(3) was not sensitive to relative humidity levels of 30 and 60%. NO(3) uptake experiments involving substrates of levoglucosan, abietic acid, and the mixture exhibit an initial strong uptake of NO(3) followed by NO(3) gas-phase recovery as a function of NO(3) exposure. In contrast, the uptake of NO(3) by nitroguaiacol continuously proceeds at the same efficiency for investigated NO(3) exposures. The derived oxidative power, i.e. the product of γ and atmospheric oxidant concentration, for applied oxidants is similar or significantly larger in magnitude than for OH, emphasizing the potential importance of these oxidants for particle oxidation. Estimated atmospheric lifetimes for the topmost organic layer with respect to O(3), NO(2), N(2)O(5), and NO(3) oxidation for typical polluted conditions range between 1-112 min, indicating the potential for significant chemical transformation during atmospheric transport. The contact angles determined prior to, and after heterogeneous oxidation by NO(3), representative of 50 ppt for 1 day, do not decrease and thus do not indicate a significant increase in hygroscopicity with potential impacts on water uptake and cloud formation processes.     

Rate constants of the reaction of NO3 with CH3I measured with use of cavity ring-down spectroscopy

We have applied cavity ring-down spectroscopy to a kinetic study of the reaction of NO3 with CH3I in 20-200 Torr of N2 diluent at 298 K. The rate constant of the reaction of NO3 + CH3I was determined to be (4.1 +/- 0.2) x 10(-13) cm3 molecule(-1) s(-1) in 100 Torr of N2 diluent at 298 K and is pressure-independent. This reaction may significantly contribute to the formation of reactive iodine compounds in the atmosphere.     

A study of the reaction of N+ with O2: experimental quantification of NO+(a 3Sigma+) production (298-500 K) and computational study of the overall reaction pathways

The product branching ratios for NO+(X 1Sigma+) and NO+(a 3Sigma+) produced from the reaction of N+ with O2 have been measured at 298 and 500 K in a selected ion flow tube. Approximately 0.5% of the total products are in NO+(a) at both temperatures, despite the fact that the reaction to form NO+(a) is 0.3 eV exothermic. High-level ab initio calculations of the potential energy surfaces for the N+ + O2 reaction show that the reaction from N+(3P) + O2(3Sigma(g)) reactants starts with an efficient early stage charge transfer to the N(2D) + O2+(X 2Pi) channel, which gives rise to the O2+(X 2Pi) product and, at the same time, serves as the starting point for all of the reaction channels leading to NO+ and O+ products. Pathways to produce NO+(a 3Sigma+) are found to be less favorable than pathways leading to the major product NO+(X 1Sigma+). Production of N(2D) has implications for the concentration of NO in the mesosphere.     

Relationship between the ratio of ligand to metal and the coordinating ability of anions. Synthesis and structural properties of AgX-bearing bis(4-pyridyl)dimethylsilane (X- = NO2-, NO3-, CF3SO3-, and PF6-)

Studies of the anion effects on the molecular construction of a series of AgX complexes with bis(4-pyridyl)dimethylsilane (L) (X- = NO2-, NO3-, CF3SO3-, and PF6-) have been carried out. Formation of the skeletal bonds appears to be primarily associated with a suitable combination of bidentate N-donors of L and a variety of coordination geometries of Ag(I) ions. The L:Ag(I) ratios of the products are dependent on the nature of the polyatomic anions. The 1:1 adduct Ag(I)-L for NO2-, 3:4 adduct for NO3-, 2:3 adduct for CF3SO3-, and 1:2 adduct for PF6- have been obtained. A linear relationship between the ratio of ligand to metal and the coordinating ability of anions was observed. [Ag(NO2)(L)] has a unique sheet structure consisting of double helices, and [Ag3(L)4](NO3)3 is a 2 nm thick interwoven sheet structure consisting of nanotubes. The compound [Ag2(L)3](CF3SO3)2 affords a characteristic ladder-type channel structure, and [Ag(L)2](PF6) is a simple 2D grid structure.     

Kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 in the temperature range 220-360 K

The kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 have been studied in direct measurements at temperatures between 220 and 360 K using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated at 193 or 248 nm by pulsed laser photolysis of appropriate precursors. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of NO2 being in large excess over radical concentrations. The bimolecular rate coefficients of all three reactions are independent of the bath gas (He or N2) and pressure within the experimental range (1-6 Torr) and are found to depend on temperature as follows: k(CH2Cl + NO2) = (2.16 +/- 0.08) x 10(-11) (T/300 K)(-1.12+/-0.24) cm3 molecule(-1) s(-1) (220-363 K), k(CHCl2 + NO2) = (8.90 +/- 0.16) x 10(-12) (T/300 K)(-1.48+/-0.13) cm3 molecule(-1) s(-1) (220-363 K), and k(CCl3 + NO2) = (3.35 +/- 0.10) x 10(-12) (T/300 K)(-2.2+/-0.4) cm3 molecule(-1) s(-1) (298-363 K), with the uncertainties given as one-standard deviations. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are about +/-25%. In the reactions CH2Cl + NO2, CHCl2 + NO2, and CCl3 + NO2, the products observed are formaldehyde, CHClO, and phosgene (CCl2O), respectively. In addition, a weak signal for the HCl formation has been detected for the CHCl2 + NO2 reaction.     

NO* release from MbFe(II)NO and HbFe(II)NO after oxidation by peroxynitrite

In this work, we showed that the reaction of peroxynitrite with MbFe(II)NO, in analogy to the corresponding reaction with HbFe(II)NO (Herold, S. Inorg. Chem. 2004, 43, 3783-3785), proceeds in two steps via the formation of MbFe(III)NO, from which NO* dissociates to produce iron(III)myoglobin (Mb = myoglobin; Hb = hemoglobin). The second-order rate constants for the first steps are on the order of 10(4) and 10(3) M(-1) s(-1), for the reaction of peroxynitrite with MbFe(II)NO and HbFe(II)NO, respectively. For both proteins, we found that the values of the second-order rate constants increase with decreasing pH, an observation that suggests that HOONO is the species responsible for oxidation of the iron center. Nevertheless, it cannot be excluded that the pH-dependence arises from different conformations taken up by the proteins at different pH values. In the presence of 1.2 mM CO2, the values of the second-order rate constants are larger, on the order of 10(5) and 10(4) M(-1) s(-1), for the reaction of peroxynitrite with MbFe(II)NO and HbFe(II)NO, respectively. The pH-dependence of the values for the reaction with MbFe(II)NO suggests that ONOOCO2- or the radicals produced from its decay (CO3*-/NO2*) are responsible for the oxidation of MbFe(II)NO to MbFe(III)NO. In the presence of large amounts of nitrite (in the tens and hundreds of millimoles range), we observed a slight acceleration of the rate of oxidation of HbFe(II)NO by peroxynitrite. A catalytic rate constant of 40 +/- 2 M(-1) s(-1) was determined at pH 7.0. Preliminary studies of the reaction between nitrite and HbFe(II)NO showed that this compound also can oxidize the iron center, albeit at a significantly slower rate. At pH 7.0, we obtained an approximate second-order rate constant of 3 x 10(-3) M(-1) s(-1).     

Reaction of NO with hypochlorous acid

The reaction between NO(g) at concentrations between 0.1 and 1.0 Torr in 1-atm N₂ and aqueous solutions of NaClO has been studied over the pH range of 6–12 and hypochlorite concentrations between 0.01 and 1.0M. A very rapid and efficient reaction occurs leading to the production of about 30%–40% of the NO as NO₂ and with conversions of NO up to 98% at about 1-sec contact time. It is shown that a fast chain reaction initiated by the endothermic step can account for the data. The very exothermic reaction NO + ClO^? → NO₂ + Cl^? is shown to be at least 30-fold slower than i. The overall reaction seems very promising as a method of reducing NO and NO₂ emissions from the exhausts of industrial plants.     

S型Sb2WO6/g-C3N4复合光催化剂及其增强的可见光诱导的光催化氧化NO性能

近年来,随着工业化和城镇化的飞速发展,作为一种典型的空气污染物,NOx已经造成严重的环境问题,甚至威胁到人类的身体健康.为了解决这个问题,科研工作者研发了许多NOx去除技术,其中光催化技术被认为是一种能有效地去除空气中NOx的技术.作为一种廉价、无毒、热稳定性强、能带结构合适的光催化材料,石墨相氮化碳(g-C3N4)能够有效的利用可见光,将NO光催化氧化为NO3^-.但是由于自身的光生载流子复合率较高,光谱响应范围较窄等缺点,g-C3N4不能有效的光催化去除空气中持续流动的低浓度NO,限制了其在光催化领域中的实际应用.因此,有必要合成出高催化活性、高光响应范围的S型复合光催化剂来克服以上光催化材料的不足.为此,我们利用超声辅助法制备了一系列的S型Sb2WO6/g-C3N4复合光催化剂,呈现出优异的光催化活性:与其纯组分相比,所制备的15-Sb2WO6/g-C3N4复合光催化剂在可见光下照射30 min,可去除68%以上的持续流动的NO(初始浓度400 ppb),且五次循环实验后,Sb2WO6/g-C3N4复合光催化剂仍然具备良好的光催化活性和稳定性.透射电子显微镜结果清楚地表明,Sb2WO6颗粒已成功地均匀地负载到g-C3N4纳米片表面.紫外可见漫反射光谱的结果表明,Sb2WO6和g-C3N4的复合可以有效地提高对可见光的吸收能力.与纯g-C3N4样品相比,复合样的吸收带边具有明显的红移.光致发光光谱结果表明,在Sb2WO6/g-C3N4复合半导体中,光生载流子的复合受到抑制.光电流与电阻抗分析可知,与纯Sb2WO6和g-C3N4相比较,在15-Sb2WO6/g-C3N4复合光催化剂中的光生载流子的迁移速率和分离效率较高.通过对样品的能带结构分析并已有参考文献,我们认为Sb2WO6和g-C3N4的接触边界形成了S型异质结,使光生载流子的转移速率更快,改善了光生电子-空穴对分离,而且增强可见光的利用效率,从而提高了光催化性能.自由基捕获实验结果证实,?O2^-主导了Sb2WO6/g-C3N4复合光催化剂去除NO反应,h^+也在一定程度上参与了光催化氧化NO的反应.通过原位红外光谱技术研究了Sb2WO6/g-C3N4光催化NO氧化的反应机理,研究发现,Sb2WO6/g-C3N4复合光催化剂光催化去除是氧诱导的反应.具体反应机理是在可见光的驱动下,光催化剂表面的光生电子会与被吸附的O2反应生成?O2^-,并与光生h^+一起,共同将低浓度的NO光催化氧化为亚硝酸盐或硝酸盐.该研究有助于深入研究光催化氧化NO机理,并为设计高效光催化剂用于光催化氧化ppb级NO提供了一种极具前景的策略.     

Time-programmed peptide helix inversion of a synthetic metal complex triggered by an achiral NO3- anion

Dynamic and efficient inversion of peptide helices by an achiral NO3- anion was programmed in terms of time scale from milliseconds to hours.