光敏络合催化光解水析氢的电化学模拟

Durham等^[1]曾利用Pt(黑)|lN HCl‖Ru(bipy)₃²⁺、MV²⁺、EDTA(pH=9)|Pt(网)电池模拟光解水析氢反应。但该装置的左、右二半电池中溶液的pH值相差9以上,相当于外加0.5V以上的偏压,因此,不能真实地模拟自发的光解水析氢过程。     

阳离子交换型聚合物AQ薄膜修饰碳纤维电极及伏安行为

本文成功地制备了Eastman-AQ-55D聚合物修饰碳纤维电极,用循环伏安法探讨了一些实验参数的影响,并对Ru(NH₃)₆³⁺、甲基紫精进行了分析,结果表明,AQ-55D修饰的微电极稳定性好,修饰方法简单,灵敏度和选择性都有一定的提高,Ru(NH₃)₆³⁺、甲基紫精的峰电流与浓度在1.2×10^-6～1.2×10^-5mol/L、1.7×10^-6～1.4×10^-5mol/L范围内呈线性关系,其相关系数分别为0.999、0.998.利用此电极测定了几种离子在膜中的扩散系数.     

8-羟基喹啉合十钒酸盐的研究(Ⅲ)——锂、钾、铵盐的合成、鉴定与性质

在合成与研究钠盐的基础上^[1,2],我们又合成了锂、钾和铵盐,通过元素分析、分子量测定、质谱分析、X射线衍射、紫外和红外吸收光谱分析和热重分析确定了新化合物的组成与化学式并推测了化合物的结构式。     

氧化石墨阳离子交换容量测定过程中结构的变化

氧化石墨(GO)结构层上的碳羟基(―C―OH)和边缘羧基(―COOH)在水介质中发生质子化反应解离出的H+具有阳离子可交换性。实验采用甲醛缩合法测量了GO的阳离子交换容量(CEC),用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)分析测试手段对GO阳离子交换过程中间产物的结构变化进行了分析。结果表明,GO的CEC高达541.48 mmol/100 g。NH_4~+和Ca~(2+)交换后的GO,保持稳定的层状结构,c轴方向层间距分别增大了0.1499和0.2905 nm。NH_4+和Ca~(2+)主要以层间可交换阳离子形式存在于层间域中,并与水分子形成可交换水化阳离子层,部分以[NH_4(H_2O)_6]+和[Ca(H_2O)_6]_2+的形式存在于结构层的边缘附近,共同平衡结构层水解产生的负电荷。     

NH3R++NHR2(R=H,CH3)体系质子传递反应的从头算研究

用从头计算法在HF/6-31G^*基组水平上研究了NH₄⁺+NH₃→NH₃+NH₄⁺,NH₄⁺+NH₂CH₃→NH₃+NH₃CH₃⁺,NH₄⁺+NH(CH₃)₂→NH₃+NH₂(CH₃)₂⁺以及NH₃CH₃⁺+NH₂CH₃→NH₂CH₃+NH₃CH₃⁺等4个体系的质子传递反应的机理.结果表明:(1)上述质子传递反应均具有双阱型的势能面,质子沿N(1)、N(2)连线直接传递;(2)质子受体分子中的甲基对质子传递起促进作用,而质子给体离子中的甲基则阻碍质子的传递。     

Ion chromatography of organic-rich natural waters from peatlands II. Na, NH4, K, Mg and Ca

Organic rich natural waters from peat bogs in continental (Switzerland) and maritime (Shetland Islands, Scotland) environments were analysed for Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺ using ion chromatography. These cations were determined simultaneously in surface and pore water samples from the continental bogs using a 250-μl injection loop in an isocratic separation. Using this loop, detection limits of the order of 1 ng/g were achieved. An organics-removal cartridge (Dionex OnGuard P) was used to remove humic materials. Analyses of deionized water filtered through these cartridges showed acceptably low blank values (e.g., ca. 5 ng/g) and appeared to have no significant effect on the measured cation concentration. For the maritime bog waters, the low concentrations of NH₄⁺ (ca. 1 μg/g) compared with Na⁺ (ca. 100 μg/g) required improved peak separation. This was accomplished using a gradient separation beginning with 40 mM HCl—1 mM , -2,3-diaminopropionic acid monochloride (DAP) and switching to 40 mM HCl-12 mM DAP after 2 min. Using a 25 μl injection loop, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺ were determined simultaneously in less than 25 min. In this instance, even with Na⁺/NH₄⁺ > 100, there was no interference from Na⁺ in the determination of NH₄⁺ (baseline separated).     

X-ray diffraction, Raman study and electrical properties of the new mixed compound [Rb0.44(NH4)0.56]2HgCl4 · H2O

Differential scanning calorimetry of [Rb_0.44(NH₄)_0.56]₂HgCl₄ · H₂O material showed three anomalies at 340, 355 and 424 K, respectively. The room temperature phase has space group Pcma (a=8.433(1) Å, b=9.1817(9) Å and c=11.954(1)). Phase II (T=350 K) is disordered and exhibits orthorhombic symmetry (a=8.456(13), b=9.202(9) and c=12.011(10) Å). Hydrogen bonding, the nature and the degree of structure (dis)order and the mechanisms of the transitions are discussed. The dielectric constant ^′ at different frequencies and temperature revealed a phase transition at T=340 K related to NH₄⁺ reorientation and H⁺ diffusion, and a characteristic increase above 355 K, which might be due to loss of water of crystallization. Transport properties in this compound appear to be due to an Rb⁺/NH₄⁺ and H⁺ ions hopping mechanism.     

Kinetic mass spectrometric determination of the absolute rate coefficient for the reaction NH3 (ν = 0) + NH3 → NH4 + NH2 at thermal kinetic energies

The absolute thermal rate coefficient for the reaction NH₃⁺ + NH₃ → NH₄⁺ + NH₂ has been determined experimentally for the first time for NH₃⁺ (ν = 0) reactant ions. An increase in E_vib results in a decrease in the rate coefficient for proton transfer.     

Structural Characterizations of Spherical Octadecavanadates Encapsulating Na+, K+ or I- and Ellipsoidal Octadecamolybdate Encapsulating two Anions of SO42-

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/Na₂S_x (or (NH₄)₂S_x) 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)₂S_x, 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.     

明胶保护的铂在联吡啶钌体系中光助催化分解水产氢的研究

以联吡啶钌络合物Ru(bipy)₃²⁺为光敏剂,甲基紫精MV²⁺为电子交换的中继物,EDTA为电子给体,氯铂酸钾为催化剂,探讨了该体系在可见光照射下,光还原水产氢的结果。提出了用明胶作为铂催化剂的稳定剂,可以提高放氢的速度和保护催化剂不受破坏。讨论了该体系光助催化分解水产氢的可能的机理。     

几种光还原水催化体系产氢量子收率的研究(Ⅱ)

在光解水制氢研究中,光产氢量子收率是一个重要参数。太阳能的光化学储存效率主要取决于光敏催化体系的光波长吸收范围和效率以及所得预期产物的量子收率,即光反应生成产物的分子数与体系吸收的光子数的比值。     

A New Mechanism for the Formation of the Ozone Hole in the Earth Atmosphere

It is generally accepted that the Earth ozone layer is depleted by chlorine atoms produced via solar photolysis of chlorofluorocarbons (CFCs) in the upper stratosphere^[1]. This photodissociation model predicts an ozone depletion maximum at an altitude between 30 and 40 km and negligible ozone depletion below 20 km^[1]. However, the Antarctic/Arctic ozone hole appearing in each spring is observed to be located at an altitude of about 15 km^[2]. The formation of the ozone hole has been attributed to heterogeneous reactions on the surface of polar stratosphere clouds (PSCs) consisting mainly of condensed water ice:HCl+ClONO₂→Cl₂+HNO₃^[3,4]. Recently, it has been observed that dissociation of CFCs by capture of low-energy electrons is enhanced by several orders of magnitude when CFCs are adsorbed on the surfaces of ice films of polar molecules such as H₂O and NH₃^[5,6]. This enhancement is due to transfer of electrons in precursors of solvated states in polar molecular ice to CFCs that then dissociate^[7]. This effect should be most efficient in the lower stratosphere of about 15 km, where low-energy electrons can be produced by cosmic-ray ionization and localized in precursors of solvated electrons in PSCs^[8]. Strong and straightforward evidence of this new mechanism for ozone depletion has also been found in data obtained from field measurements (satellites, balloons, etc.)^[8]. In this talk, we will present the data from both field and laboratory measurements and discuss the new mechanism for the formation of the ozone hole.     

Ion-exchange properties of hypercrosslinked polystyrene impregnated with methyl orange

A novel bipolar stationary phase (HCPS–MO) was prepared by impregnation of hypercrosslinked polystyrene (HCPS) with methyl orange (MO; 4-dimethylamino-4′-sulfoazobenzene) and its ion-exchange properties were studied. Simultaneous separation of cations and anions on HCPS–MO is possible, although it behaves preferentially as a cation-exchanger. Unusual selectivity of HCPS-MO for alkali and alkaline-earth metal cations: Na⁺+K⁺+4⁺+ and Mg²⁺2+2+2+ was observed. The effect of temperature on retention of alkali and alkaline-earth metal cations was studied. Separation of Na⁺, K⁺, Rb⁺, NH₄⁺, Cs⁺, Mg²⁺ and Ca²⁺ on HCPS–MO with diluted cerium(III) nitrate solution as an eluent in single run is presented.     

Voltammetric determination of glucose based on reduction of copper(II)–glucose complex at lanthanum hydroxide nanowire modified carbon paste electrodes

A novel voltammetric method for the determination of β-d-glucose (GO) is proposed based on the reduction of Cu(II) ion in Cu(II)(NH₃)₄²⁺–GO complex at lanthanum(III) hydroxide nanowires (LNWs) modified carbon paste electrode (LNWs/CPE). In 0.1 mol L⁻¹ NH₃·H₂O–NH₄Cl (pH 9.8) buffer containing 5.0 × 10⁻⁵ mol L⁻¹ Cu(II) ion, the sensitive reduction peak of Cu(II)(NH₃)₄²⁺–GO complex was observed at −0.17 V (versus, SCE), which was mainly ascribed to both the increase of efficient electrode surface and the selective coordination of La(III) in LNW to GO. The increment of peak current obtained by deducting the reduction peak current of the Cu(II) ion from that of the Cu(II)(NH₃)₄²⁺–GO complex was rectilinear with GO concentration in the range of 8.0 × 10⁻⁷ to 2.0 × 10⁻⁵ mol L⁻¹, with a detection limit of 3.5 × 10⁻⁷ mol L⁻¹. A 500-fold of sucrose and amylam, 100-fold of ascorbic acid, 120-fold of uric acid as well as gluconic acid did not interfere with 1.0 × 10⁻⁵ mol L⁻¹ GO determination.     

直径大于2nm的(15, 15)碳纳米管的仿生生物改性及其脱盐行为的分子模拟

模仿水通道蛋白结构在直径大于2 nm的(15, 15)的碳纳米管内壁添加不同数量的―NH₃⁺和―COO^-,并结合端口改性建立连续的碳纳米管膜模型,利用分子动力学模拟方法研究了水以及Na⁺和Cl^-在碳纳米管中的通量、密度分布和离子进入碳纳米管的平均力势。结果表明,在200 MPa压力下,对碳纳米管进行内壁和端口改性可以在保持较高水通量基础上显著提高碳纳米管的截盐作用。当在(15, 15)碳纳米管内壁添加5对―COO^-和―NH₃⁺基团或内壁添加4对―COO^-和―NH₃⁺且端口添加1对时, Cl^-截盐率可达到100%, Na⁺的截盐率达到88%。改性(15, 15)碳纳米管的最小水通量仍是未改性(8, 8)碳纳米管的4.6倍。     

SO_4~(2-)功能化处理对Fe_2O_3催化剂上氨选择性催化还原NO_x性能的促进机理研究

采用沉淀法制备了Fe(OH)_3和Fe_2O_3。通过硫酸化处理得到SO_4~(2-)/Fe(OH)_3和SO_4~(2-)/Fe_2O_3两种催化剂,并将其应用于氨选择性催化还原NO_x(NH_3-SCR)反应,研究了SO_4~(2-)功能化处理对Fe_2O_3催化剂上NH_3-SCR脱硝性能的促进机理。结果表明,与纯的Fe_2O_3相比,硫酸化处理得到的催化剂上SCR活性得到显著提升;其中,SO_4~(2-)/Fe(OH)_3表现出更加优异的催化性能,在250-450℃时NO_x转化率高于80%,且具有优异的稳定性和抗H_2O+SO_2性能。XRD、Raman、TG、FT-IR、H_2-TPR、NH_3-TPD和in situ DRIFTS等表征结果显示,硫酸功能化处理能抑制Fe_2O_3的晶粒生长,同时SO_4~(2-)与Fe~(3+)结合形成硫酸盐复合物,提高了催化剂表面酸性位点的数量和酸强度,抑制了Fe_2O_3上的氨氧化反应,从而提高了其脱硝催化性能。     

芘四硫酸四钠盐/甲基紫精复合物光物理性质的研究

本文通过吸收光谱滴定和时间分辨瞬态吸收光谱对芘四硫酸四钠盐(pyrenetetrasulfonic acid tetrasodium salt,PyTS)/甲基紫精(methylviologen,MV²⁺)复合物在水溶液中的光物理性质进行研究。用甲基紫精滴定芘四硫酸四钠盐时,得到该复合物的组成成份是1:1,反之,用芘四硫酸四钠盐滴定甲基紫精时,同样得到1:1组成成份的复合物。该复合物的形成常数是2.4×10⁶mol^-1·L,当用光激发该复合物时,发现其中存在芘四硫酸四钠盐到甲基紫精的电子转移过程,并得到该过程的动力学模型。     

Ammonia sorption by Dawson acid studied by IR spectroscopy and microbalance

Using in-situ microbalance and infrared spectroscopy techniques the double ammonia proton complexation was traced. The results confirm the formation of N₂H₇⁺ dimer in solid Dawson acid H₆P₂W₁₈O₆₂, previously reported only for N₂H₇I and for (N₂H₇)₄SiW₁₂O₄₀. The formation of such dimers was evidenced by the microbalance results, the molar ratio of ammonia to proton was measured as 2:1 at 10.7 kPa and 298 K. The formation of NH₄⁺ monomer (band at 1410 cm⁻¹) and N₂H₇⁺ dimer (1460 cm⁻¹) was revealed by IR spectroscopy. Enthalpy of ammonia sorption on Dawson structure was calculated to be −127.9 kJ mol⁻¹, indicating the lower acid strength of Dawson-type compared to that of the Keggin-type heteropolyacids, like H₄SiW₁₂O₄₀.     

Vibrational dependence of the NH3 (v2)+NO and NO(v)+NH3 charge transfer cross sections

A tandem quadrupole mass spectrometer is used to study the charge transfer reactions NH₃⁺ + NO and NO⁺ + NH₃ over a collision energy range 1.5–13 eV. The vibrational state of the reagent ions is selected by resonance-enhanced multiphoton ionization. For the 0.9 eV exothermic process NH₃⁺ + NO → NH₃ + NO⁺ excitation of the v₂ umbrella bending mode (v₂ = 0–12) causes no marked change in the charge transfer cross section, while in the reverse process NO⁺ + NH₃ → NO + NH₃⁺ excitation of the NO⁺ vibration (v = 0–6) strongly enhanced the charge transfer cross section.     

Simultaneous determination of anions and cations by ion-exclusion chromatography–cation-exchange chromatography with tartaric acid/18-crown-6 as eluent

Ion-exclusion chromatography–cation-exchange chromatography was developed for the simultaneous separation of common inorganic anions and cations (Cl⁻, NO₃⁻ and SO₄²⁻; Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) on a weakly acidic cation-exchange column by elution with weak acid. Generally, the resolution among these monovalent cations was only moderate, thereby hindering the determination of these analytes in natural-water samples. Therefore, 18-crown-6 was added to the eluent to improve the resolution. A good separation of these anions and cations on a weakly acidic cation-exchange column was achieved in 30 min by elution with 5 mM tartaric acid/6 mM 18-crown-6/methanol–water (7.5:92.5). The ion-exclusion chromatography–cation-exchange chromatography method developed here was successfully applied to the separation of major anions and cations in an environmental water sample.