Novel Bi-Doped Amorphous SnOx Nanoshells for Efficient Electrochemical CO2 Reduction into Formate at Low Overpotentials

Engineering novel Sn-based bimetallic materials could provide intriguing catalytic properties to boost the electrochemical CO₂ reduction. Herein, the first synthesis of homogeneous Sn_1−xBi_x alloy nanoparticles (x up to 0.20) with native Bi-doped amorphous SnO_x shells for efficient CO₂ reduction is reported. The Bi-SnO_x nanoshells boost the production of formate with high Faradaic efficiencies (>90%) over a wide potential window (−0.67 to −0.92 V vs RHE) with low overpotentials, outperforming current tin oxide catalysts. The state-of-the-art Bi-SnO_x nanoshells derived from Sn_0.80Bi_0.20 alloy nanoparticles exhibit a great partial current density of 74.6 mA cm⁻² and high Faradaic efficiency of 95.8%. The detailed electrocatalytic analyses and corresponding density functional theory calculations simultaneously reveal that the incorporation of Bi atoms into Sn species facilitates formate production by suppressing the formation of H₂ and CO.     

甲醛与甲酸甲酯的偶联反应 Ⅰ.杂多酸的催化作用

研究了４种杂多酸（磷钨酸、硅钨酸、磷钼酸和硅钼酸）对甲醛和甲酸甲酯偶联反应的催化作用；对反应条件进行了考察。结果表明，磷钨酸和硅钨酸对该反应具有较高的催化活性；而氧化性强的钼系杂多酸的活性较低。水对甲醛和甲酸甲酯的偶联反应具有不利影响。将杂多酸在３００℃进行热处理后，其活性显著增强。     

UO_2(HCOO)_2·H_2O在290K-10K的红外光谱及~(235)U-~(238)U同位素位移的研究

本文通过测定甲酸铀酰[UO_2(HCOO)_2·H_2O]在290K-10K的红外光谱,确定了该化合物铀酰基团(O-U-O)v_(as)振动峰位,研究了温度对峰宽、峰位的影响,并采用差减及峰内标法估算了甲酸铀酰在290K-10K的同位素位移值。测得290K,77K及10K时~(238)U的v_(as)值分别为931.90cm~(-1),930.82cm~(-1)和930.74cm~(-1),~(235)U-~(238)U同位素位移△v分别为0.63cm~(-1),0.67±0.18cm~(-1)和0.71±0.21cm~(-1),位移值与理论计算值接近。     

Behavioral and electrophysiological activity of (Z,E)-7,9,11-dodecatrienyl formate,a mimic of the major sex pheromone component of carob moth,Ectomyelois ceratoniae

The behavioral and electrophysiological activity of a mimic [(Z,E)7,9,11-dodecatrienyl formate] of the major sex pheromone component [(Z,E) 9,11,13-tetradecatrienal] of carob moth was assessed. Wind-tunnel bioassays demonstrated that the formate was as effective as natural gland extracts, and significantly more effective than the trienal alone or than the trienal blended with two minor pheromone components, in evoking source contact. Dispensers containing the formate were as effective as trienal-containing blend lures in attracting males when placed at the same dosage in traps in date gardens. Single-cell recordings showed that at least two olfactory neurons, differentiated by spike amplitude, are located in the long trichoid hairs on male carob moth antennae. Dose-response relationships indicated that puffs from cartridges loaded with at least 0.1 g of the formate or of the trienal were necessary to elicit spiking by either the small or the large-spiking cell within a sensillum. Cross-adaptation studies demonstrated that both compounds stimulated the same large-spiking cell. The frequencies of spikes evoked from the large cell when stimulated by emissions from 0.1-g, 1-g, or 10-g cartridges of either the formate or the trienal were not significantly different, suggesting that the formate is an effective mimic of the trienal at the antennal receptor cell level.     

甲醇氧化酯化反应的Mo－Sb－O催化剂研究

探讨了采用Ｍｏ－Ｓｂ－Ｏ复合氧化物催化剂，由甲醇的氧化酯化反应合成甲酸甲酯。文中考察了反应温度、催化剂晶格、接触时间对甲醇转化率的影响，测试了催化剂性能，扼要探讨了该催化反应的机理。     

含水混酸的酯化分离试验

基于中国石化扬子石化公司化工厂醋酸装置产生大量的含水甲酸、乙酸副产品,通过试验将含水混酸进行酯化、分离,得到符合工业品规格的甲酸乙酯、乙酸乙脂。试验确定酯化塔回流比为3∶1,乙醇分批次加入,乙醇实际投入量与理论量的比为1.2。酯化分离结果:甲酸乙酯的单程收率89.5%,纯度大于97%,乙酸乙酯的单程收率80.1%,纯度大于97%。     

净化黄磷尾气合成甲酸甲酯研究

用净化黄磷尾气为原料与甲醇液相合成甲酸甲酯 ,并对影响一氧化碳及甲醇转化率、甲酸甲酯时空收率等的因素进行了研究。研究结果表明 ,随着主催化剂浓度或反应压力的增大 ,一氧化碳转化率及甲醇转化率均提高 ;助剂的加入可以大大提高甲酸甲酯时空收率和延长催化剂的寿命。优化的反应条件为 :主催化剂 (甲醇钠 )浓度 0 .4mol L ;助催化剂吡啶浓度 1.74mol L ;温度 80℃ ;时间 160min ;压力 4MPa。在此条件下 ,黄磷尾气中一氧化碳及甲醇转化率可分别达到 95 .5 %和 43%。     

An Attractive Synthetic Approach to Methyl Formate from Methanol via Methyl Nitrite

Catalytic synthesis of methyl formate has been investigated by a novel route starting from methyl nitrite in vapor phase. The acidic sites of the catalysts play a crucial role for the catalytic activity and the selectivity of formation of methyl formate. The H-Y zeolite catalyst gave higher yield and selectivity of the target product. This study provides a new approach for the synthesis of methyl formate from methanol via methyl nitrite.     

甲酸甲酯合成与转化的催化技术

本文评述了甲酸甲酯(MF)合成与转化的催化技术,展示了从MF出发发展C_1化学的可能途径,在MF的合成方面详细地分析了从甲醇出发的羰化法、脱氢法和氧化法催化技术,简介了我们的有关研究工作。     

吡啶为助剂合成甲酸甲酯的动力学研究

在60～90℃对以吡啶为助催化剂由一氧化碳合成甲酸甲酯的反应进行了动力学研究。结果表明该反应为2级反应,速率方程rυ=-dpco/dt=k[MOH]pco,无助催化剂时反应活化能Ea=67.63kJ/mol,反应速率常数k=9.66×106exp(-67.63×103/RT)(mol-1·L·min-1);当有助催化剂存在时,反应活化能为Ea=61.19kJ/mol,反应速率常数k=8.82×106exp(-61.19×103/RT)(mol-1·L·min-1)。并对助催化剂吡啶的助催化机理进行了探讨。