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1.
由于发生歧化离解,Mo2O3(S2CNEt2)4的溶液不遵守Beer定律,我们测定了有关溶液的光吸收性质以及Mo2O3(S2CNEt2)4的歧化离解常数,于15℃时数值为2.2×10-4。  相似文献   

2.
M. M. Taqui Khan 《Polyhedron》1983,2(12):1247-1260
Dichlorotetrakis(dimethylsulphoxide)ruthenium(II) reacts with AsPh3 AsMePh2, AsMe2Ph and SbPh3 in ethanolic hydrochloric acid solution to yield the complexes RuCl2(DMSO)2(AsPh3)2, RuCl2(DMSO) L2 (L = AsMePh2, AsMe2Ph, SbPh3) respectively. The treatment of ruthenium(II) blue solution with AsMePh2, AsMe2Ph and SbPh3 in alcohol resulted in the formation of the complexes; RuCl2L3 (L = AsMePh2, AsMe2Ph and SbPh2), respectively. The reaction of RuCl2(DMSO)4 with the bidentate ligands 1,2 bis (diphenylarsino)methane (DPAM), 1,2 bis(diphenylarsino)ethane (DPAE) and 1,2 bis (diphenylphosphino)methane (DPPM). 1,2 bis(diphenylphosphino)ethane (DPPE), in ethanol gave the complexes RuCl2(DPAM)2, RuCl2(DPAE)2, RuCl2 (DPPM)2 RuCl2(DPPE)2, respectively. The complexes thus obtained undergo reaction with carbon monoxide, hydrogen, molecular nitrogen and nitric oxide to yield a variety of mixed ligand complexes.  相似文献   

3.
基于微波水热法和微乳液法合成SnO2/TiO2纳米管复合光催化剂.通过X射线衍射(XRD)、配有能量色散X射线光谱仪(EDX)的透射电镜(TEM)和电化学手段对光催化剂进行表征.以甲苯为模型污染物,考察光催化剂在紫外光(UV)和真空远紫外光(VUV)下的性能及失活再生.结果表明,SnO2/TiO2纳米管复合光催化剂形成三元异质结(锐钛矿相TiO2(A-TiO2)/金红石相TiO2(R-TiO2)、A-TiO2/SnO2和R-TiO2/SnO2异质结),促使光生电子-空穴对的有效分离,提高光催化活性.SnO2/TiO2表现出最佳的光催化性能,UV和VUV条件下的甲苯降解率均达100%,CO2生成速率(k2)均为P25的3倍左右.但由于UV光照矿化能力不足,中间产物易在催化剂表面累积.随着UV光照时间的增加,SnO2/TiO2逐渐失活,20 h后k2由138.5 mg·m-3·h-1下降到76.1 mg·m-3·h-1.利用VUV再生失活的SnO2/TiO2,过程中产生的·OH、O2-·、O(1D)、O(3P)、O3等活性物质可氧化吸附于催化剂活性位的难降解中间产物,使催化剂得以再生,12 h后k2恢复到143.6 mg·m-3·h-1.UV和VUV的协同效应使UV降解耦合VUV再生成为一种可持续的光催化降解污染物模式.  相似文献   

4.
Photolysis of compounds of the type [Re(CCMe2R)(OR′)2] (R = Me or Ph; OR′ = O′Bu, OCMe2(CF3), or OCMe(CF3)2) in benzene with a medium pressure mercury lamp yields compounds of the type [Re(OR′)2]2(μ-CCMe2R)2 in an intramolecular and irreversible manner. [Re(CCMe2R)(OR′)2]2 and [Re(OR′)2]2(μ-CCMe2R)2 (OR′ = O′Bu or OCMe2(CF3)2) both react with excess carbon monoxide in several solvents to afford the dimers [Re(OR′)2(CO)]2(μ-CCMe2R)2 quantitatively. An X-ray study of [Re(OtBu)2(CO)]2 (μ-CtBu)2 shows it to consist of two distorted trigonal bipyramids connected by two symmetrically bridging neopentylidyne ligands. The unbridged dimers of general formula [Re(CCMe2R)(OR′)2]2 do not react readily with simple substrates such as phosphines, olefins, or acetylenes, although [Re(CCMe2R)(OtBu)2]2 can be oxidized by iodine to yield Re(CCMe2R)(OtBu)2I2 in good yield. In contrast, {Re[OCMe(CF3)2]2}2(μ-CtBu)2 reacts with one equivalent of phenylacetylene to give a species in which one of the two bridging alkylidyne ligands is retained.  相似文献   

5.
The diol R2C(SiMe2OH)2 (R = Me3Si) has been shown to react with: SO2Cl2 to give R2 Me2; SOCl2 to give R2C(SiMe2Cl)2; Me3SiI or Me3SiCl to give R2C(SiMe2OSiMe3)2; R′COCl; (R′ = Me or CF3) to give R2C(SiMe2O2CR′)-(SiMe2Cl); (R′CO)2O (R′ = Me or CF3 to give R2C(SiMe2O2CR′)2; with MeOH containing acid to give R2C(SiMe2OMe)2; with neutral MeOH to give R2C-(SiMe2OMe)2 and probably R2 Me2; MeLi to give R2C(SiMe2OLi)2 (and the latter to react with PhMeSiF2 to give R2 Me2). The diacetate R2C(SiMe2O2CMe)2 reacts with CsF in MeCN to give R2C(SiMe2F)2; it does not react with NaN3 or KSCN in MeCN, but the bis(trifluoroacetate) reacts with these salts with KOCN to give R2C(SiMe2X)2 (X = N3, NCS, NCO).  相似文献   

6.
The stabilities of the hydrated uranyl phosphates (UO2)3(PO4)2 · 4 H2O, UO2HPO4 · 4 H2O, and UO2(H2PO4) · 3 H2O have been reinvestigated. The compounds identified by thermal analysis have been prepared isothermally and characterized by their strongest X-ray reflections. During dehydration, oxygen was not evolved and the crystalline compounds (UO2)3(PO4)2, (UO2)2P2O7, UO2(PO3)2, and probably (UO2)3P4O)13 were found.

At still higher temperatures, the uranyl phosphates are reduced. The decomposition products lose phosphorus oxide above 1300–1400°C. The present results are summarized in a tentative pseudo-binary phase diagram UOx(x = 3 to 2)—UO2(PO3)2.  相似文献   


7.
The binuclear molybdenum(II) complexes [Mo2(O2CCF3)4(PR3)2] (R = Ph, Et) act as templates for the self-condensation of 2-aminobenzaldehyde to give a new class of complexes in which a hydride ion bridges two molybdenum(III) centres, each of which carries a tetradentate macrocyclic ligand (C). The new hydrido complexes [Mo2(C)2 (H)(O2CCF3)3(PPh3)2] (I), [Mo2(C)2(H)2(O2CCF3)2(PPh3)2] (II), and [Mo2(C)2 (H)2(O2CCF3)2(PEt3)2]2 (V) exist in two or more isomeric forms as shown by their IR, 1H, 31P and 19F NMR spectra. Substitution with thiocyanate, nitrate and tetraphenylborate anions gives the new products [Mo2(C)2(H)(CO)(NCS)3(PPh3)2] (III), [Mo2(C)2 (H)2(O2CCF3)(NO3)(PPh3)2] (IV), [Mo2(C)2(H)(O2CCF3)(PPh3)2](BPh4)2 (VI) and [Mo2(C)2(H)2(O2CCF3)(PEt3)2](BPh4) (VII), which also exist in isomeric forms.  相似文献   

8.
利用热天平对比研究了大同煤及煤焦在O2/N2、O2/CO2和O2/H2O/CO2中的燃烧行为,探讨CO2和H2O气化反应对其富氧燃烧特性的影响。结果表明,在5%氧气浓度下,煤粉在O2/N2、O2/CO2和O2/H2O/CO2中的燃烧速率按顺序依次降低。氧气浓度降低到2%,由于CO2和H2O气化反应的作用,煤粉在高温区的整体反应速率按顺序依次增大。当氧气浓度为5%时,煤焦在O2/CO2中的燃烧速率要低于O2/N2中的燃烧速率,但燃烧反应推迟后气化反应的参与使得煤焦在O2/H2O/CO2中的整体反应速率显著升高。当氧气浓度降低到2%后,随着温度的升高,在CO2气化反应的作用下,煤焦在O2/CO2中的整体反应速率逐渐高于O2/N2中的燃烧速率。在O2/H2O/CO2中,由于H2O在共气化中起主要作用,煤焦在O2/H2O/CO2高温区的整体反应速率进一步升高。动力学分析表明,在5%氧浓度时,煤焦在O2/N2、O2/CO2和O2/H2O/CO2中的表观活化能依次升高。随着氧气浓度的降低,在不同反应气氛中的表观活化能均有所下降。  相似文献   

9.
The tetrathiomolybdate ion [MoS4]2− reacts in DMF solution with Roussin esters Fe2(SR)2(NO)4 (R = Me, Et, n-Pr, i-Pr, n-Bu,t-Bu, n-C5H11) to yield the paramagnetic iron nitrosyls [Fe(NO)2(SR)2] (1), [Fe(NO)2(S2MoS2] (2) and [Fe(NO)(S2MOS2)2] (3). The new complexes (2) and (3) have been characterized by EPR spectroscopy and the assignment to them of constitutions based respectively upon tetrahedral and square pyramidal iron is supported by EHMO calculations. Fe2(SPh)2(NO)4 with [MoS4]2− yields only [Fe(NO)2(SPh)2], and preformed (3) reacts with PhS to give firstly EPR-silent species, and then [Fe(NO)2(SPh)2]. The mononitrosyl (3) can also be formed by reaction of [MoS4]2− with [Fe4S3(NO)7], Fe4S4(NO)4, or Fe2I2(NO)4.  相似文献   

10.
采用工业用V2O5-WO3/TiO2催化剂,基于傅里叶原位红外光谱(FT-IR)技术考察SO2的氧化过程及烟气组分对SO2氧化行为的影响;结果表明,SO2在催化剂表面氧化主要是首先吸附在催化剂表面V2O5活性位上,占据其O原子,以SO2-3形式存在,后与催化剂表面V5+-OH发生反应,生成金属硫酸盐(VOSO4)中间产物,O2重新氧化催化氧化过程中由于被SO2夺取O原子而被还原的V2O5物种,使V4+转化为V5+,促进金属硫酸盐(VOSO4)向SO3转化;SO2与NO、NH3的竞争吸附阻碍SO2在V2O5活性点位上的氧化;在SCR中,NO的脱除与SO2的氧化是相互抑制的关系。  相似文献   

11.
Experiments were carried out to investigate the removals of SO2 and NOx from simulated lignite-burning flue gas containing SO2 (4800 ppm), NO (320 ppm) and H2O (22%) by electron beam irradiation. Removal efficiencies of SO2 and NOx were achieved to reach 97 and 88% at 70°C, and 74 and 85% at 80°C, respectively, with the dose of 10.3 kGy without NH3 leakage. The higher removal efficiencies of SO2 and NOx were observed in simulated lignite-burning flue gas than in coal-fired flue gas containing 800 ppm of SO2, 225 ppm of NO and 7.5% H2O at the same treatment condition. The higher removal efficiencies were attributed to the higher concentrations of SO2, H2O, and added NH3. Simulation calculations indicated that the higher concentrations of these components enhance the effective radical reactions to oxidize NO to form NO2 with HO2 radical, and to oxidize SO2 to form SO3 with OH radical and O2. The reactions of NOx with N and NH2 radicals to produce N2 and N2O also promote the NOx removal. By-product was determined to be the mixture of (NH4)2SO4 and NH4NO3 containing a small amount of H2SO4.  相似文献   

12.
Polyoxoanions of tungsten, molybdenum, and vanadium have been the subject of interest since their wide variety of compositions, structures, and properties give rise to numerous important applications[1]. From the NH4VO3/Na2Sx (or (NH4)2Sx) reaction system we synthesized several spherical octadecavanadates with Na+,K+, NH4+ or I encapsulated using hydrothermal method. These complexes include (NH4)11[V18O42(Na)]·(H2O)20 1; (NH4)11[V18O42(K)]·(H2O)6, 2; (NH4)10(Na)[V18O42(Na)]·(H2O)26, 3; (NH4)11[V18O42(NH4]·(H2O)20, 4; and (NH4)20(I)7[V18O42(I)]·(H2O)12, 5, in which the structures of 1, 2, 3, and 5 have been determined by X-ray analyses. In the analogous reaction system of (NH4)2MoS4/(NH4)2Sx, we also obtained one ellipsoidal octadecamolybdate, (NH4)4[Mo18O54(2SO4)]·(H2O)4, 6 with a standard Wells-Dawson structure[2]. The Ortep drawings of the two kinds of structures are viewed as follows.  相似文献   

13.
Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF3(CF2)7(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)7CF3, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF3(CF2)5(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)5CF3, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF3(CF2)3(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)3CF3, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured.  相似文献   

14.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P = (PPh3)2, Ph2P(CH2)3PPh2, Phd2P(CH2)4PPh2; 1,4-dithiols = HS(CH2)4SH, (−)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-l-threitol), BINASH2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph2P(CH2)3PPh2, Ph2P(CH2)4PPh2; dithiolato = S(CH2)4S, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh3)2] and [Pd(S(CH2)4S)(Ph2P(CH2)3PPh2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC12 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%.  相似文献   

15.
异质结型光催化膜的活性及其机理研究   总被引:11,自引:0,他引:11  
采用浸渍提拉法制得TiO2,ZnO,Fe2O3,ZnO/TiO2,TiO2/ZnO,Fe2O3/TiO2和TiO2/Fe2O3石英玻璃基底负载膜.光催化降解亚甲基蓝实验表明,TiO2和ZnO具有良好的光催化活性,Fe2O3活性较差.但形成异质结后,TiO2和Fe2O3的光催化降解能力发生明显的变化.用254nm紫外光光照后,TiO2,ZnO和Fe2O3等3种氧化物膜与水的接触角均有不同程度的降低,TiO2表现出超亲水性,ZnO/TiO2和Fe2O3/TiO2膜与水的接触角小于对应的单纯ZnO和Fe2O3膜与水的接触角,其中Fe2O3/TiO2表面出现超亲水性.瞬态光电导谱的少数载流子寿命的测定表明,异质结势垒电场能有效地增强光生电子-空穴对的分离效率.根据能带理论建立的两组异质结能带模型可合理地解释实验结果.  相似文献   

16.
Separation of acetylene(C2H2) from carbon dioxide(CO2) by adsorbents is very challenging owing to their high similarity on molecular shape and dimension. Exploring inexpensive and easily available porous materials is of importance to facilitate the practical implementation of the challenging but energy-efficient separation. Herein, we utilize an easily available porous material[Zn3(HCOO)6] for the selective separation of C2H2 over CO2. Because of the pore confinement in[Zn3(HCOO)6](pore size of 0.47 nm) and accessible oxygen sites for preferential binding of C2H2, this material exhibits high low-pressure uptake for C2H2(63 cm3/cm3 at 10 kPa and 298 K) and high C2H2/CO2 selectivity(7.4 under ambient conditions) that is comparable to those of out-performing porous materials. The efficient separation of[Zn3(HCOO)6] for C2H2/CO2 mixture has also been confirmed by the breakthrough experiments.  相似文献   

17.
Complexes trans-[PtX(L)(PPh3)2]A [1: X = CF3; A = BF4; L = NCNH2, NCNMe2, NCNEt2, or NCNC(NH2)2. 2: X = Cl; A = BPh4; L = NCNMe2 or NCNEt2] and cis-[PtCl(L)(PPh3)2][BPh4] [3: L = NCNH2 or NCNC(NH2)2], which appear to be the first cyanamide or cyanoguanidine complexes of platinum to be reported, have been prepared by treatment of trans-[PtBr(CF3)(PPh3)2] (in CH2Cl2/acetone and in the presence of Ag[BF4]) or of cis-[PtCl2(PPh3)2] (in THF and in the presence of Na[BPh4]), respectively, with the appropriate substrate. In KBr pellets or in solution 1 (L = NCNMe2 or NCNEt2) undergoes ready replacement of the organocyanamide (under the trans influence of CF3) by bromide to regenerate trans-(PtBr(CF3)(PPh3)2]. The X-ray structure of 1 (X = CF3, A = BF4, L = NCNEt2) is also reported, and shows the presence of two apical intramolecular contacts of the metal with two ortho-hydrogen atoms of the phosphines, whereas the amine N atom of the diethylcyanamide is trigonal planar in the linear NCN framework with a delocalized π system.  相似文献   

18.
Photochemical reaction of (CO)2(dppe)Fe(H)(SiR3) with HSiR3 (SiR3 = Si(OMe)3, Si(OEt)3, SiMe3, SiMe2Ph, SiPh3) yields the trihydrido silyl complexes (CO)(dppe)FeH3(SiR3 ). The analogous complexes (PR′Ph2)3 FeH3(ER3) are prepared by reaction of the H2 -complexes (PR′Ph2)3FeH2(H2) with HER3 (ER3 = SiMe3, SiMC2Ph, SiMePh2, SiPh3, Si(Me2)OSi(Me2)H, SnPh3, SnEt3). Additional derivates of (CO) (dppe)FeH3(SiR3) (SiR3 = SiMePh2) and (PR′Ph2)3FeH3(SiR3) (SiR3 = Si(OMe)3, SiH2Ph, SiHPh2, Si(OEt)3, SiMePhCl) are accessible by silane exchange starting from (CO)(dppe)FeH3(SiMe3) and (PR′Ph2) 3FeH3(SiMe3). (PBuPh2)3FeH3(SiMePh2) was also prepared from (PBuPh2)3FeH2(N2) and HSiMePh2, and (PBuPh2)3FeH3(SnMe3) from (PBuPh2)3FeH2(H2) and Me3SnCl. The complex (PBuPh2) 3FeH3(SnMe3) crystallizes as a toluene solvate in the cubic space group I 3d and shows crystallographically imposed C3-symmetry. The complexes (CO)2 (dppe)Fe(H)(SiR3) and (PR′Ph2)3FeH3(ER3) are highly dynamic in solution. Low temperature NMR measurements and the E, Fe, H coupling constants strongly indicate that the exchange mechanism involves η2-HER3 ligands.  相似文献   

19.
Closo-BnHn−2(CO)2 (n = 5–12), isolobal analogues of closo-C2Bn−2Hn, have been investigated at the B3LYP/6-311+G**density functional level of theory. The most stable isomers of closo-BnHn−2(CO)2 are similar to those of closo-C2Bn−2Hn in geometric patterns apart from closo-B6H4(CO)2, and closo-BnHn−2(CO)2 is much less strained than closo-C2Bn−2Hn. Energetic analysis identifies closo-B6H4(CO)2, closo-B12H10(CO)2 and closo-B10H8(CO)2 to be most stable, of which the latter two cages have been prepared experimentally. On the basis of the negative and rather large nucleus independent chemical shifts (NICS), closo-BnHn−2(CO)2 are aromatic. To aid further experimental study, the CO stretching frequencies have been computed.  相似文献   

20.
Cp2MoH2 reacts with methyl acrylate in the presence of acetylenes (L = C2H2, C2Me2, HCCtBu, HCCSiMe3, C2(SiMe3)2, HCCCH2OMe, HCCCH2NMe2) to form acetylene complexes Cp2Mo(L) 5. Protonation takes place with CF3CO2H at −80°C to give short-lived cations [Cp2MoH(L)+ (8) (L = C2Me2, HCCSiMe3, C2(SiMe3)2). The structure of [Cp2MoH{η2-C2(SiMe3)2}]PF6(9) was determined by an X-ray diffraction study.  相似文献   

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