5-(苯并-15-冠-5)-10,15,20-碘化三(对三甲铵苯基)卟啉铑、钌、钯配合物的合成

合成了一种水溶性的５－（苯并－１５－冠－５）－１０，１５，２０－碘化三（对三甲铵苯基）卟啉及其与铑、钌、钯的３种新配合物。进行了元素分析、电子光谱、ＩＲ、１ＨＮＭＲ表征和光助还原水放Ｈ２的实验。     

5，10，15，20－四（4－羟基－3－磺酸苯基）卟啉光度法测定水中痕量铜的研究

在ｐＨ４．０时，铜与标题试判形成１：１的配合物．作工曲线回归方程为Ｙ＝３．０５×１０（－３）＋０．２３１Ｘ，相关系数ｒ＝０．９９９１，其最大吸收波长在４１２ｕｍ处，摩尔吸光系数ε＝２．０３×１０５Ｌ·ｍｏｌ（－１）·ｃｍ（－１）．用含量在０～２．０μｇ／２５ｍｌ范围内符合朗伯比耳定律．     

－（4’－甘缬二肽苯基）－10，15，20－三苯基卟啉的合成

本文报道了５－（４′－甘缬二肽苯基）－１０，１５，２０－三苯基卟啉的合成。经ＵＶ、ＩＲ、￣１ＨＮＭＲ、ＭＳ和元素分析鉴定了结构。     

尾式5—{对—[2—（2—甲乙基）—1，3—二恶烷]苯氧基}—10，15，20—三苯基卟啉及其金属配合物的合成与表征

2－（2－甲乙基）－1，3－二恶烷与存在无水K2CO3的DMF的溶剂中的5－（4－羟基苯基），10，15，20－三苯基卟啉反应，合成了一新种型卟啉5－{对－[2－（2－甲乙基）－1，3－二恶烷]苯氧基}－10，15，20－三苯基卟啉，并据此制得了锌、钯、钌配合物，对化合物的结构分别用UV－Vis,IR,^1HNMR三元分析等手段进行了表征。     

meso-四-(4-辛氧基-3-甲氧基苯基)卟啉及其金属配合物的合成与表征

报道了一种新型对称型卟啉化合物meso-四-(4-辛氧基-3-甲氧基苯基)卟啉(TOMPPPH2)及其金属钌、钯配合物(Ru(DMF)2TOMPPP,PdTOMPPP)的合成,并通过可见光谱,红外光谱,核磁共振氢谱和元素分析等对这些卟啉化合物的结构进行了表征。     

5,10,15,20-四(4-羧基苯基)卟啉及其钯(Ⅱ)配合物的合成与表征

合成了5,10,15,20-四(4-羧基苯基)卟啉配体,并与氯化钯反应得到钯配合物.采用元素分析、电导测定、紫外-可见光谱、红外光谱、核磁共振和电喷雾质谱等多种物理手段表征了配体及其钯配合物的结构,对配合物的空间构型和成键性质进行了讨论,研究了配合物在氮气气氛中的热分解行为.该配合物属于低自旋的平面正方形,配合物中离域π键和螫合环的形成使Pd-N键加强,配合物很稳定.     

5-（ρ-β-乙酸乙酯基氨基苯基）-10，15，20-三苯基卟啉络钴（Ⅱ）的合成与表征

5-(对-氨基苯基)-10,15,20-三苯基卟啉在无水碳酸钾和无水碘化钾催化下与氯乙酸乙酯进行亲核取代反应得到5-(ρ-β-乙酸乙酯基氨基苯基)-10,15,20-三苯基卟啉产率8.5%;其与Co(CH3COO)2反应得到5-(ρ-β-乙酸乙酯基氨基苯基)-10,15,20-三苯基卟啉络钴(Ⅱ),产率88.0%,其结构经UV-vsible、FT-IR、IHNMR和元素分析进行表征.     

Surface reactions of nitrogen oxide and ethylene on rhodium (111)

Temperature programming of NO and C₂H₂ coadsorbed on Rh(111) gives rise to the desorption of a number of gases. Where H₂, H₂O, CO₂ and N₂ are the main products at low C₂H₂ coverages, significant amounts of HCN, CO and NO evolve at higher C₂H₄ coverages. Static SIMS indicates the formation of a large supply of adsorbed CN species, part of which desorbs as HCN, while the remainder decomposes and is responsible for delayed formation of N₂. For the highest C₂H₄ coverages the majority of the initially adsorbed NO desorbs as HCN.     

Immobilization of HRh(CO)(P(m-C6H4SO3Na)3)3 on an anion exchange resin for the hydroformylation of higher olefins

The anion exchange resin Amberlyst, A-26, forms an efficient matrix for the immobilization of the water soluble complex, HRh(CO)(m-C₆H₄SO₃Na)₃)₃. Catalysis proceeds in anhydrous alcohol solvents which allows the conversion of water insoluble olefins to aldehydes. Activities and selectivities are similar to both supported aqueous phase catalysts and to the neutral complex, HRh(CO)(PPh₃)₃ in non-aqueous solvents. The catalyst preparation minimizes the quantity of water in the supported catalyst; the lack of water is thought to be responsible for an increase in catalyst stability toward oxidation.     

2,2-双(3-苯基-4-羟基苯基)丙烷的合成研究

以邻苯基苯酚和丙酮为原料,盐酸为催化剂,巯基丙磺酸为助催化剂,通过缩合反应合成了2,2-双(3-苯基-4羟基苯基)丙烷(双OPP-A),研究了原料配比、催化剂用量、反应温度、反应时间等因素对反应的影响,通过实验确定了合成双OPP-A的最优条件为:n(邻苯基苯酚):n(丙酮):n(盐酸):n(巯基丙磺酸)=8:2:4:1,反应温度为60℃,反应时间24h,双OPP-A收率达到78.5%,经重结晶纯度达99.2%。产物通过红外光谱和核磁共振等进行了确证。     

Studies on the synthesis of sodium ates (NaH2PO4, Na2HPO4, Na3PO4) using membrane electrolysis

Comparative studies have been carried out on the electrosynthesis of sodium phosphates in the cathode compartment of an industrial membrane cell supplied with phosphoric acid of concentrations ranging from 1 to 2 mol dm^–3. The anode compartment of the cell was supplied with brine containing 25% NaCl. Du Pont Nafion^® membranes of types N-423, N-901 and N-961 were used. It was found that current efficiencies for the production of sodium phosphates exceeded 96%, this being higher than that for sodium hydroxide and, in spite of the different properties of the membranes, these efficiencies were similar. With N-423 membrane, the current efficiency was 2 3% lower than that for other membranes, but at the same time, the voltage of the cell was lower by 8 12%. Thus, N-423 membrane gives better performance during sodium phosphate synthesis as compared to membranes N-901 and N-961.     

染料中间体N,N'-1,4-苯基二-(3-氨基-4-甲氧基)苯磺酰胺的合成

以邻氨基苯甲醚、乙酸酐、氯磺酸、对苯二胺为原料,经乙酰化、氯磺化、酰胺化、脱乙酰基等步骤,研究合成了无致癌性染料中间体N,N'-1,4-苯基二-(3-氨基-4-甲氧基)苯磺酰胺。考察了影响酰胺化反应的因素,其优化条件为:反应物用量n(4-甲氧基-3-乙酰氨基-苯磺酰氯)∶n(对苯二胺)为2.2∶1(摩尔比),反应在40°C进行,反应时间为5.0h。产率可达88.46%。产品经红外、核磁、质谱、元素分析等测定确证了结构。     

5－（3，5－二溴－2－吡啶基）－1－（2－羟基－5－磺苯基）－3－（2－羟基苯基）甲的合成及其与铜显色反应的研究

介绍了显色剂５－（３，５－二溴－２－吡啶基）－１－（２－羟基－５－磺苯基）－３－（２－羟基苯基）甲（ＢＰＨＰＳ）的合成。详细研究了试剂与铜的显色反应，其灵敏度较高，摩尔吸光系数ε为２．４６×１０４。采用掩蔽方法，能显著提高体系的选择性。用拟定的方法测定了铜矿中的铜，结果令人满意。     

Hydrogen chemisorption on Pt/Al2O3: dependence of hydrogen desorption behaviour on its surface concentration,on adsorption temperature and on surface water

The hydrogen chemisorption on Pt/Al₂O₃ was investigated by temperature programmed desorption. The activation energy of desorption strongly depends on the hydrogen surface coverage. The chemisorption process is shown to be activated. High temperature H₂ desorption (spilled-over hydrogen) is due to reoxidation of reduced parts of the carrier surface by water or -OH groups.     

多孔g-C3N4基光催化材料的制备及应用研究进展

多孔g-C₃N₄基光催化材料由于具有较高的比表面积、丰富的反应活性位点和较短的电子传递路径等特点,能较好地解决块体g-C₃N₄基材料存在的比表面积小、光生载流子复合快及可见光利用效率低等问题,因而具有广阔的发展前景和应用潜力。本文主要从以下方面进行综述：多孔g-C₃N₄基光催化材料常用的制备方法,包括硬模板法、软模板法、水热合成法、热聚合法、超分子自组装法;多孔g-C₃N₄基材料在光催化领域的应用,包括光解水制氢、光催化降解有机污染物、光催化去除氮氧化物和光催化还原CO₂等;最后指出了当前影响多孔g-C₃N₄基光催化材料发展的关键问题,并对其在光催化领域的应用前景进行了展望。     

Electrosynthesis of hydrogen peroxide in acidic solutions by mediated oxygen reduction in a three-phase (aqueous/organic/gaseous) system Part I: Emulsion structure, electrode kinetics and batch electrolysis

The mediated electrosynthesis of H₂O₂ in acidic solutions (pH 0.9–3.0) was investigated in a three-phase, aqueous/organic/gaseous system using 2-ethyl-9,10-anthraquinone (EtAQ) as mediator (redox catalyst). The main hydrogen peroxide producing route is the in situ mediating cycle: EtAQ electroreduction–homogeneous oxidation of anthrahydroquinone (EtAQH₂). The organic phase was composed of tributylphosphate solvent (TBP) with 0.2 M tetrabutylammonium perchlorate (TBAP) supporting electrolyte, 0.06 M tricaprylmethylammonium chloride (A336) surface active agent, and 0.1–0.2 M EtAQ mediator. Part I of this two part work deals with the physico-chemical characteristics of the emulsion electrolyte (e.g., ionic conductivity, emulsion type, H₂O₂ partition between the aqueous and organic phases), and kinetic aspects (both electrode and homogenous) of the mediation cycle. Furthermore, batch electrosynthesis experiments are presented employing reticulated vitreous carbon cathodes (specific surface area 1800 m² m^–3) operated at superficial current densities of 500–800 A m^–2. During 10 h batch electrolysis involving the emulsion mediated system with O₂ purge at 0.1 MPa pressure, H₂O₂ concentrations in the range 0.53–0.61 M were obtained in 0.1 M H₂SO₄ (pH 0.9) and 2 M Na₂SO₄(acidified to pH3). The corresponding apparent current efficiencies were from 46 to 68%. Part II of the present work describes investigations using flow-by fixed-bed electrochemical cells with co-current upward three-phase flow.     

New and convenient synthesis of (R)-(+)-4, 5-Dihydro-4-methyl-2(3H)-furanone and (R)-(-)-4-Bromo-3-methyl-1-O-tert-butyldimethyl-silylbutan-1-ol

A convenient partial synthesis of the lactone (+)- 10 is reported starting from the readily available methyl (S)-(+)-3-hydroxy-2-methylpropanoate (+)- 1 . Furthermore, an efficient three step route to the optically active saturated isoprene unit (-)- 13 in high yield starting from the lactone (+)- 10 is reported for the first time.