H_2O_2氧化N_2生成N_2O和H_2O机理的研究

采用量子化学计算方法研究了Ｈ２Ｏ２ 氧化Ｎ２ 生成Ｎ２Ｏ 和Ｈ２Ｏ 的机理．结果发现, Ｈ２Ｏ２ 氧化Ｎ２ 先通过１ 个四元环过渡态形成中间体Ｈ２Ｎ２Ｏ２ 分子,Ｈ２Ｎ２Ｏ２ 再通过一个五元环过渡态形成Ｎ２Ｏ和Ｈ２Ｏ．根据计算得到的每步反应的活化能,得知Ｈ２Ｏ２ 氧化Ｎ２ 生成中间体Ｈ２Ｎ２Ｏ２ 分子是整个反应的控制步骤．     

Na2O2与NO2不反应吗

通过实验验证,指出了一些期刊涉及Na2O2吸收CO2和NO混合气体的规律性等文章的知识性错误,认为习题训练中应回避此类问题,或是以此问题对学生置疑,引导学生实验探究,进行批判性教学。     

Rh2CO2/Al2O3上H2吸附及CO和H2共吸附

CO加氢反应机理一直是许多化学工作者感兴趣的课题．Rh催化剂因其优良的性能而被用于 CO加氢机理研     

C2v对称性簇Ru2N2的理论计算

采用密度泛函(B3LYP)方法计算了Ru2的部分低能电子组态，得到Ru2基态的电子谱项为7Δu，平衡核间距re=0.228 nm，振动频率ωe=338 cm－1，离解能De=1.92 eV. 同时计算了具有C2v对称性的Ru2N2簇中氮的活化情况，得到了各个优化几何构型下的键参数和体系能量.计算结果表明，氮氮键的活化程度由Ru2对氮起反馈作用的轨道数目决定.一般来说，氮氮键活化越强，体系能量越高，在相同的活化程度下，自旋多重度高的体系较稳定.     

SrSiO2N2∶Eu2+荧光粉的制备及性能研究

以SrCO3,Si3N4,Eu2O3为原料,在N2气氛下,采用自还原高温固相法制备了SrSi2O2N2:Eu2+荧光粉.研究了该荧光粉的物相结构、发光性能和晶体形貌,同时对比在不同气氛下合成的荧光粉.结果表明,在N2气氛与N2/H2气氛下分别合成的SrSi2O2N2:Eu2+荧光粉物相结构和光谱特性基本一致.显示出合成了主晶相SrSi2O2N2,但还含有少量未知的中间项.Eu2+浓度的变化不影响激发状态,而发射光谱的波长在Eu2+浓度为l mol％～20mol％之间,从530 nm的绿光红移至550 nm的黄绿光区域.同时,激发光谱覆盖的范围宽,均能有效的被UV或蓝光激发,这意味着该类荧光粉在白光LED方面有可能得到广泛的应用.     

Synthesis and Structural Characterization of Cu（pic）2[CO（NH2）2]2 and （picH2）2[Cu（pic）2（SCN）2]

1 INTRODUCTION The picolinic acid (picH), also called pyridine- 2-carboxylic acid, has a broad spectrum of physio- logical effects on the activity functions of both ani- mal and plant organisms. It is attributed increasing interest due to its ability to …     

响应面法优化H2O2/K2S2O8深度处理印染废水

结合常州市新区某纺织印染厂现有工艺,采用H2O2/K2S2O8深度处理印染废水,探讨了Fe2+浓度、H2O2/K2S2O8摩尔比、pH值和反应时间对COD去除率的影响规律.采用Box-Behnken响应面法优化反应条件并拟合出回归模型,预测COD去除率在最佳反应条件(pH=3.1、Fe2+浓度=0.97 mmol·L-...     

ZrO2-TiO2-CeO2的制备及其在NH3选择性催化还原NO中的应用

采用共沉淀法制备了载体材料TiO2、ZrO2-TiO2及ZrO2-TiO2-CeO2, 并利用X射线衍射(XRD)实验、比表面积测定(BET)、程序升温脱附(NH3-TPD)、储氧性能测定(OSC)及程序升温还原(H2-TPR)等方法对三种载体材料进行了表征. 结果表明, ZrO2-TiO2-CeO2具有较多的表面强酸位, 并具有一定的储氧性能和较强的氧化还原性能. 以三种材料为载体, 制备了质量分数分别为1%、9%的V2O5、WO3的整体式催化剂. 研究了三种催化剂在富氧条件下用NH3选择性催化还原NO的催化性能. 结果表明, 以ZrO2-TiO2-CeO2为载体的催化剂在反应空速为10000 h-1, 275 ℃时, NO的转化率接近100%, 具有最好的催化活性,并有良好的应用前景。     

CuOx/TiO2光催化水蒸气还原CO2

以商品TiO2-P25为原料,通过浸渍法负载一定量过渡金属Cu,得到一系列不同含量的CuOx/TiO2光催化剂。利用X射线衍射（XRD）,X－射线光电子能谱（XPS）,BET,高分辨率透射镜（HRTEM）,X射线荧光光谱（XRF）和光致发光光谱（PL）等方法对催化剂进行了详细表征,在自建的光催化反应器中评价了气态水光催化还原CO2反应的活性和CH4收率。结果表明负载CuOx后的TiO2纳米材料光催化性能显著提高,其中1%CuOx/TiO2样品紫外光照72 h后,CH4生成量达到了24.86 µmol•gTi-1。同时,CuOx负载量、反应温度、反应时间等因素对CH4收率均有显著影响。     

CO2/H2在不同形态ZrO2上的吸附行为

利用傅立叶变换红外光谱技术(FT-IR)考察了CO2和CO2＋H2在不同形态氧化锆上的吸附和转化行为，结果表明,氧化锆的形态影响CO2的吸附形式和表面物种的生成.无定型氧化锆上主要生成碳酸氢盐和离子碳酸盐，单斜氧化锆上还出现了双齿碳酸盐，而在四方氧化锆上出现最强的线式吸附CO2，并生成聚碳酸盐.在氢气存在的条件下，单斜氧化锆上生成甲烷而在四方氧化锆上则生成甲酸盐.     

Rh—V／SiO2上H2的化学吸附方式

ＣＯ加氢反应机理是许多研究者感兴趣的课题．负载的Ｒｈ是ＣＯ加氢反应的优良催化剂．ＣＯ在Ｒｈ上吸附态的研究已有许多报道［１～７］,而对Ｈ２有关的吸附态的研究却少见报道．Ｗｏｒｌｅｙ等［８］利用高压超纯Ｈ２在２．２％Ｒｈ／Ａｌ２Ｏ３膜上首次观测到Ｒｈ—Ｈ...     

RgCo双金属催化剂的研究IV. Rh2Co2/Al2O3上的吸附中心类型及吸附性能

利用CO和NO作为双探针分子对Rh2Co2/Al2O3的吸附中心类型和吸附性能进行了详细的研究。结果表明Rh2Co2/Al2O3上存在Rh上的孪生和桥式CO吸附中心以及Co上的线式CO吸附中心。其中Rh上的孪生和桥式CO吸附中心对CO和NO的吸附性能与Rh4/Al2O3上的孪生和桥式CO中心相似。Co上的线式CO吸附中心以预吸附的CO能被NO取代, 预吸附的NO不能被CO取代而区别于Rh4/Al2O3上的Rh的线式CO吸附中心; 又以既能吸附CO又能吸附NO而不同于Co2/Al2O3和Rh+Co/Al2O3上的Co中心。与母体簇的结构相关联, 表明H2还原后的Rh2Co2/Al2O3上Rh2Co2(CO)12簇结构仍保持, 且Rh-Co相互作用强。     

Rh/Al2O3上CO和NO的吸附性能及相互作用

利用ＴＰ－ＩＲ动态方法研究了ＣＯ和ＮＯ在Ｒｈ／Ａｌ２Ｏ３上吸附性能和相互作用的动态行为，结果表明，Ｒｈ／Ａｌ２Ｏ３的孪生中心对ＣＯ的吸附强于对ＮＯ的吸会，线式和桥式中心则对ＮＯ的吸附强于对ＣＯ的吸附，ＣＯ和ＮＯ共吸附－ＴＰ（ＣＯ和ＮＯ中）－ＩＲ动态过程结果揭示出２２２４ｃｍ＾－１谱带的出现和强度的增加与孪生ＣＯ谱带以及吸附的ＮＯ谱带的强度减弱同时发生，表明是由吸附的ＮＯ和孪生ＣＯ形成Ｒｈ－ＮＣＯ。     

RhCo双金属催化剂的研究 I. RhCo双金属催化剂的金属-金属及金属-载体相互作用

利用XPS对以金属盐共浸渍制备的Rh+Co/Al2O3和Rh2Co2(CO)12为前体制备的Rh2Co2/Al2O3催化剂的金属-金属及金属-载体相互作用进行了详细研究。发现Rh+Co/Al2O3经400℃H2还原后, Rh的结合能与Rh^0的结合能接近, Co基本上以CoAl2O4状态存在, Co^0的谱峰很弱; 而Rh2Co2/Al2O3经400℃H2还原后, Rh的结合能与Rh^0接近, Co除以CoAl2O4状态存在外, 还有相当一部分以Co^0状态存在。上述结果揭示出两个样品的Rh-Al2O3的相互作用弱, Co-Al2O3的相互作用强。Rh+Co/Al2O3上Rh-Co相互作用弱, 而Rh2Co2/Al2O3在H2还原后仍保持RhCo簇合物的强的Rh-Co相互作用, 导致显著量的Co^0存在。     

Rh/ZnO-Al2O3催化剂用于巴豆醛选择性加氢（英文）

Gas phase hydrogenation of crotonaldehyde was performed over 1 wt% Rh/ZnO-Al2O3 catalysts with various Zn/Rh atomic ratios. Monometallic Rh/Al2O3 was also prepared for comparison. The samples were prepared by the successive impregnation of Al2O3 with chlo-ride precursors of zinc and rhodium. The solids have been characterized by H2 chemisorption,temperature-programmed reduction,scanning electron microscopy,and cyclohexane dehydrogenation. Their catalytic behaviour in the gas phase crotonaldehyde hydrogenation reaction after reduction treatment in flowing hydrogen at 723 K was investigated. The relationship between catalytic activity,selectivity for crotyl alcohol,and physicochemical properties of the catalysts was examined. Results obtained showed that the presence of Zn clearly promotes the hydrogenation of the carbonyl bond. The catalyst with Zn/Rh atomic ratio of 5 displayed good catalytic stability and the highest selectivity for crotyl alcohol(70%) along with alloy formation.     

NO在碳纳米管(CNTs),Rh/CNTs,Rh/Al_2O_3上的分解(英文)

甲烷在预还原的ＬａＣｏＯ３催化剂上分解生成碳纳米管（ＣＮＴｓ）。研究了稳态下ＮＯ在ＣＮＴｓ,Ｒｈ／ＣＮＴｓ,Ｒｈ／Ａ１２Ｏ３上的分解,温度区间为５７３Ｋ～９７３Ｋ,原料气为６０００ｐｐｍ的ＮＯ,Ｈｅ为平衡气。程序升温还原结果表明：（１）Ｒｈ的负载显著降低了ＣＮＴｓ的氢吸收量;（２）负载于ＣＮＴｓ上的Ｒｈ比负载于Ａ１２Ｏ３上的Ｒｈ更易还原。在５７３Ｋ时ＮＯ即能与预还原后的ＣＮＴｓ,Ｒｈ／ＣＮＴＳ,Ｒｈ／Ａｌ２Ｏ３中存储的氢反应;随着氢的消耗,反应活性逐渐降低,当储存的氢消耗完后,ＮＯ的直接催化反应发生。在８７３ Ｋ及以上,Ｒｈ／ＣＮＴｓ中的ＣＮＴｓ能彼ＮＯ分解产生的氧氧化为ＣＯ。在９７３Ｋ时,ＮＯ在ＣＮＴｓ上几乎能１００％分解,连续反应１５０ｍｉｎ后其反应活性不降低,且未观察到ＣＯ或ＣＯ２的生成。在９７３Ｋ时ＣＮＴｓ本身可作为ＮＯ分解的催化剂,这是一个非常有意义的结果。     

Electronic Structure of [Pt(2)(&mgr;-O(2)CCH(3))(4)(H(2)O)(2)](2+) Using the Quasi-Relativistic Xalpha-SW Method: Analysis of Metal-Metal Bonding, Assignment of Electronic Spectra, and Comparison with Rh(2)(&mgr;-O(2)CCH(3))(4)(H(2)O)(2)

The electronic structure and metal-metal bonding in the classic d(7)d(7) tetra-bridged lantern dimer [Pt(2)(O(2)CCH(3))(4)(H(2)O)(2)](2+) has been investigated by performing quasi-relativistic Xalpha-SW molecular orbital calculations on the analogous formate-bridged complex. From the calculations, the highest occupied and lowest unoccupied metal-based levels are delta(Pt(2)) and sigma(Pt(2)), respectively, indicating a metal-metal single bond analogous to the isoelectronic Rh(II) complex. The energetic ordering of the main metal-metal bonding levels is, however, quite different from that found for the Rh(II) complex, and the upper metal-metal bonding and antibonding levels have significantly more ligand character. As found for the related complex [W(2)(O(2)CH)(4)], the inclusion of relativistic effects leads to a further strengthening of the metal-metal sigma bond as a result of the increased involvement of the higher-lying platinum 6s orbital. The low-temperature absorption spectrum of [Pt(2)(O(2)CCH(3))(4)(H(2)O)(2)](2+) is assigned on the basis of Xalpha-SW calculated transition energies and oscillator strengths. Unlike the analogous Rh(II) spectrum, the visible and near-UV absorption spectrum is dominated by charge transfer (CT) transitions. The weak, visible bands at 27 500 and 31 500 cm(-)(1) are assigned to Ow --> sigma(Pt(2)) and OAc --> sigma(Pt(2)) CT transitions, respectively, although the donor orbital in the latter transition has around 25% pi(Pt(2)) character. The intense near-UV band around 37 500 cm(-)(1) displays the typical lower energy shift as the axial substituents are changed from H(2)O to Cl and Br, indicative of significant charge transfer character. From the calculated oscillator strengths, a number of transitions, mostly OAc --> sigma(Pt-O) CT in nature, are predicted to contribute to this band, including the metal-based sigma(Pt(2)) --> sigma(Pt(2)) transition. The close similarity in the absorption spectra of the CH(3)COO(-), SO(4)(2)(-), and HPO(4)(2)(-) bridged Pt(III) complexes suggests that analogous spectral assignments should apply to [Pt(2)(SO(4))(4)(H(2)O)(2)](2)(-) and [Pt(2)(HPO(4))(4)(H(2)O)(2)](2)(-). Consequently, the anomalous MCD spectra reported recently for the intense near-UV band in the SO(4)(2)(-) and HPO(4)(2)(-) bridged Pt(III) complexes can be rationalized on the basis of contributions from either SO(4) --> sigma(Pt-O) or HPO(4) --> sigma(Pt-O) CT transitions. The electronic absorption spectrum of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] has been re-examined on the basis of Xalpha-SW calculated transition energies and oscillator strengths. The intense UV band at approximately 45 000 cm(-)(1) is predicted to arise from several excitations, both metal-centered and CT in origin. The lower energy shoulder at approximately 40 000 cm(-)(1) is largely attributed to the metal-based sigma(Rh(2)) --> sigma(Rh(2)) transition.     

A fourth isolated oxidation level of the [Mn12O12(O2CR)16(H2O)4] family of single-molecule magnets

The Mn12 family of single-molecule magnets (SMMs) has been extended to a fourth isolated member. [Mn12O12(O2CR)16(H2O)4] (1) exhibits three quasi-reversible one-electron-reduction processes at significantly higher potentials than [Mn12O12(O2CMe)16(H2O)4]. This has allowed the previous generation and isolation of the one- and two-electron-reduced versions of 1 to now be extended to the three-electron-reduced complex. For cation consistency and better comparisons, the complete series of complexes has been prepared with NPrn4+ counterions. Thus, complex 1 was treated with 1, 2, and 3 equiv of NPrn4I, and this led to the successful isolation of (NPrn4)[Mn12O12(O2CCHCl2)16(H2O)4] (2), (NPrn4)2[Mn12O12(O2CCHCl2)16(H2O)4] (3), and (NPrn4)3[Mn12O12(O2CCHCl2)16(H2O)4] (4), respectively. Another three-electron-reduced analogue (NMe4)3[Mn12O12(O2CCHCl2)16(H2O)4] (5) was prepared by the addition of 3 equiv of NMe4I to 1. Direct current magnetization data were collected on dried microcrystalline samples of 2-5 and were fit by matrix diagonalization methods to give S = 19/2, D = -0.35 cm(-1), and g = 1.95 for 2; S = 10, D = -0.28 cm(-1), and g = 1.98 for 3; S = 17/2, D = -0.25 cm(-1), and g = 1.91 for 4; and S = 17/2, D = -0.23 cm(-1), and g = 1.90 for 5, where D is the axial zero-field splitting parameter. Thus, the [Mn12]3- complexes 4 and 5 possess significantly decreased absolute magnitudes of both S and D as a result of the three-electron addition to 1, which has S = 10 and D = -0.45 cm(-1). The D value of the series 1-4/5 shows a monotonic decrease with electron addition that is consistent with the progressive loss of MnIII ions, which are the primary source of the molecular anisotropy. Nevertheless, when studied by ac susceptibility techniques, the [Mn12]3- complexes still exhibit frequency-dependent out-of-phase susceptibility signals at < or =2.5 K, indicating them to be single-molecule magnets (SMMs), albeit at lower temperatures compared with 1 (6-8 K range), 2 (4-6 K range), and 3 (2-4 K range); the shifts to lower temperatures reflect the decreasing S and D values upon successive reduction and hence the decreasing energy barrier to magnetization relaxation. Thus, the [Mn12]3- complexes represent a fourth isolated oxidation level of the Mn12 family of SMMs, by far the largest range of oxidation levels yet encountered within single-molecule magnetism.     

Rh/Al_2O_3-Cr_2O_3整体式催化剂的制备和二氯甲烷催化氧化性能

以粉末Al_2O_3为载体,通过浸渍Rh(NO_3)_3制备Rh/Al_2O_3催化剂;再以Rh/Al_2O_3、粉末Cr_2O_3和铝胶经过研磨混合制得催化剂活性浆料;将催化剂活性浆料涂覆到堇青石蜂窝陶瓷载体表面,经烘干,焙烧制得不同Rh含量的Rh/Al_2O_3-Cr_2O_3系列整体式催化剂.研究了该类催化剂的二氯甲烷催化氧化性能,发现Rh负载量为0.4 g/L的Rh/Al_2O_3-Cr_2O_3催化剂活性最佳,且未生成含氯中间产物.结合催化剂的表征结果发现,Rh的添加可增加催化剂的表面酸性和氧化还原性能,二者的协同作用提高了催化剂活性;而Cr_2O_3的存在有利于CH_3Cl中间体的进一步氧化,从而提高了催化剂的选择性.