Heterogeneous Catalytic Partial Oxidation of C3-C4 Alkanes with Nitrogen Monoxide

The possibility of making products of partial oxidation, alcohols and acids in particular, by the reaction of C₃-C₄ alkanes with nitrogen monoxide over oxide and zeolite catalysts is demonstrated. The most effective catalysts are CeO₂ and Fe-TsVK. The dependence of the rate and selectivity of the process on the reaction conditions has been established.     

Electrochemical Oxidation of Nitrogen towards Direct Nitrate Production on Spinel Oxides

Nitrates are widely used as fertilizer and oxidizing agents. Commercial nitrate production from nitrogen involves high‐temperature‐high‐pressure multi‐step processes. Therefore, an alternative nitrate production method under ambient environment is of importance. Herein, an electrochemical nitrogen oxidation reaction (NOR) approach is developed to produce nitrate catalyzed by ZnFe_xCo_2?xO₄ spinel oxides. Theoretical and experimental results show Fe aids the formation of the first N?O bond on the *N site, while high oxidation state Co assists in stabilizing the absorbed OH^? for the generation of the second and third N?O bonds. Owing to the concerted catalysis, the ZnFe_0.4Co_1.6O₄ oxide demonstrates the highest nitrate production rate of 130±12 μmol h^?1 g_MO^?1 at an applied potential of 1.6 V versus the reversible hydrogen electrode (RHE).     

Influence of Periodic Nitrogen Functionality on the Selective Oxidation of Alcohols

An enhancement in catalytic alcohol oxidation activity is attributed to the presence of nitrogen heteroatoms on the external surface of a support material. The same Pd particles (3.1–3.2 nm) were supported on polymeric carbon–nitrogen supports and used as catalysts to selectively oxidize benzyl alcohol. The polymeric carbon–nitrogen materials include covalent triazine frameworks (CTF) and carbon nitride (C₃N₄) materials with nitrogen content varying from 9 to 58 atomic percent. With comparable metal exposure, estimated by X‐ray photoelectron spectroscopy, the activity of these catalysts correlates with the concentration of nitrogen species on the surface. Because the catalysts showed comparable acidic/basic properties, this enhancement cannot be ascribed to the Lewis basicity but most probably to the nature of N‐containing groups that govern the adsorption sites of the Pd nanoparticles.     

Psychotropic Preparations Sydnophen and Sydnocarb as Donors of Nitrogen Monoxide

The metabolic chain of the antihypertensive drug Molsydomin, which belongs to the group of sydnonimine derivatives, was modelled in vitro with the psychotropic drugs Sydnophen and Sydnocarb, which are also derivatives of sydnonimine. Like Molsydomin, Sydnophen and Sydnocarb are hydrolyzed to N-nitroso compounds which liberate nitrogen monoxide, NO, on subsequent oxidation which may be related to the pharmacological effects of these drugs.     

富氢气中CO氧化脱除研究

富氢气中少量的CO会导致燃料电池电极中毒,质子交换膜燃料电池 (PEMFC) 的发展急需解决该问题。目前以催化氧化脱除富氢气中少量CO是较理想的方式。本文概述了富氢气中CO选择性氧化脱除的研究进展,并展望了今后研究的方向及应用前景。     

Intermediates in the Autoxidation of Nitrogen Monoxide

ONOO^. is an important intermediate in the autoxidation of nitrogen monoxide by dioxygen. A formerly unknown red isomer of N₂O₄, ONOONO (see figure), formed in 2‐methylbutane at 113 K from nitrogen monoxide and dioxygen, is converted to O₂NNO₂ upon warming.

     

非贵金属催化剂上CO氧化的研究与进展

非贵金属催化剂催化CO氧化反应研究,不仅拓展了非贵金属的应用,而且为探求可替代贵金属催化CO氧化反应的催化剂提供了新机遇,成为当前催化研究中的热点课题之一。本文综述了近年来铜、钴等非贵金属催化剂体系催化CO氧化反应的研究进展。     

非贵金属催化剂上CO氧化的研究与进展

非贵金属催化剂催化CO氧化反应研究,不仅拓展了非贵金属的应用,而且为探求可替代贵金属催化CO氧化反应的催化剂提供了新机遇,成为当前催化研究中的热点课题之一。本文综述了近年来铜、钴等非贵金属催化剂体系催化CO氧化反应的研究进展。     

纳氏试剂测定水中氨氮影响因素的探讨

对国家生活饮用水标准检验方法"GB/T5750—2006"中涉及到的水中氨氮的检测条件进行了探讨,讨论了样品的采集与保存,影响显色、空白值的各项因素,并提出相应的解决办法。对国家标准物质以及实际样品的验证表明,方法的相对误差为0.03%~1.5%,相对标准偏差RSD为0.55%~5.3%,准确度也能满足分析要求,对国家标准方法进行了补充与细化,在实际工作中有参考价值。     

Determination of the Total Nitrogen Content of Organic Substances Through the Ammonia Formed in Oxidation by Persulfate

Abstract

A new concept for the analytical application of persulfate oxidation in alkaline media is presented: The persulfate oxidation of organic compounds has been utilized to determine their nitrogen content. The ammonia formed in the oxidation coupled distillation was measured acidimetrically with an accuracy of ± 0.5 % (rel.). The applicability of the method proposed is shown in the determination of the organically bound nitrogen content of numerous model substances as well as industrial and natural matrices: vinasse, aluminate liquor, white- and soy-bean samples, eggprotein.     

负载金的纳米管钛酸光催化氧化一氧化碳

 用化学方法制备了负载金的纳米管钛酸(Au/H2Ti2O4(OH)2)光催化剂,并用TEM,XPS,XRD和DRS等技术对催化剂进行了表征. 结果表明,经573 K处理后,纳米管钛酸表面及管内均有零价的金颗粒存在. 与纳米管钛酸(H2Ti2O4(OH)2)相比,Au/H2Ti2O4(OH)2具有明显的CO光催化氧化活性,但在暗态时无活性. 经分析认为,暗态时Au与纳米管相互接触的周界处不活泼,故催化剂无CO催化氧化活性; 紫外光照射下,纳米管激发产生e--h+对,e-从纳米管转移到Au0上, 使纳米管和Au-在接触周界处产生相互作用,形成活性位,导致CO催化氧化反应发生.     

甲醇电化学催化氧化机理研究进展

甲醇催化氧化机理的研究对催化剂的开发具有重要的意义。本文概述了甲醇在铂表面催化氧化的反应机理;催化剂的中毒情况以及抗CO催化剂的研究进展,重点阐述了催化剂的结构和表面组成以及电极电势对催化活性的影响。目前的催化剂是不令人满意的．基础研究将有助于避免用纯经验的方法来寻求更为理想的催化剂。     

Radical C−H Acylation of Nitrogen Heterocycles Induced by an Aerobic Oxidation of Aldehydes

An aerobic radical approach for the synthesis of unsymmetrical heteroaryl ketones is described herein. The reaction involves cross‐dehydrogenative coupling between aldehydes and heteroaromatic bases with molecular oxygen (O₂). The key aspect of the method is the generation of reactive acyl radical via homolytic activation of aldehyde C?H bond using O₂ as the sole oxidant. The reaction has a good substrate scope with respect to aldehydes and functionalized nitrogen heterocycles. Based on our mechanistic studies, a radical chain pathway is suggested for the reaction. A synthetic application of the method is demonstrated in the formal synthesis of natural alkaloid (±) angustureine.     

新型晶须状氧化钛担载Au的CO催化氧化性能

从钛钾比较高的二钛酸钾晶须出发,通过离子交换和热处理等步骤制备了具有不同微观结构的晶须状TiO2,然后通过均相沉积-沉淀法在制得的TiO2上担载1%的Au.采用X射线衍射、扫描电镜、低温N2吸附-脱附及透射电镜等技术对催化剂样品进行了表征,并测定了其催化CO氧化反应性能.结果表明,600℃处理所得晶须状TiO2载体(T(600))具有丰富的介孔结构,比表面积为59 m2/g,平均孔径为11 nm,担载Au后其孔道结构保持良好,而800℃处理所得晶须状TiO2样品(T(800))孔结构完全坍塌,但仍保持纯锐钛矿晶型.在相同担载条件下Au/T(800)上的Au颗粒尺寸明显小于Au/T(600)上的,但两者催化CO氧化反应活性相差不大,CO完全转化温度分别为80和70℃,活性均比Au/P25的高.     

Ethanol Oxidation Reaction Mechanism on Gold Nanowires from Density Functional Theory

Thin gold nanowires (NWs) are materials that could be used as support in different chemical reactions. Using density functional theory (DFT) it was shown that NWs that form linear atomic chains (LACs) are suitable for stimulating chemical reactions. To this end, the oxidation reaction of ethanol supported on the LACs of Au−NWs was investigated. Two types of LACs were used for the study, one pure and the other with an oxygen impurity. The results showed that the oxygen atom in the LAC fulfills important functions throughout the reaction pathway. Before the chemical reaction, it was observed that the LAC with impurity gains structural stability, that is, the oxygen acts as an anchor for the gold atoms in the LAC. In addition, the LAC was shown to be sensitive to disturbances in its vicinity, which modifies its nucleophilic character. During the chemical reaction, the oxidation of ethanol occurs through two different reaction paths and in two stages, both producing acetaldehyde (CH₃CHO). The different reaction pathways are a consequence of the presence of oxygen in the LAC (oxygen conditions the formation of reaction intermediates). In addition, the oxygen in the LAC also modifies the kinetic behavior in both reaction stages. It was observed that, by introducing an oxygen impurity in the LAC, the activation energy barriers decrease ∼69 % and ∼97 % in the first and second reaction stages, respectively.     

双氧水氧化苯乙烯制苯甲酸的机理研究

在苯乙烯100 mmol,n(钨酸钠)∶n(草酸)∶n(苯乙烯)∶n(30%H2O2)=2.0∶3.2∶100.0∶440.0,92℃的反应条件下,用GC-MS和GC-IR跟踪分析了反应物和反应产物。根据其含量随反应时间的变化关系,提出了苯乙烯氧化为苯甲酸可能经过两条途径的反应机理。     

Photoassisted Catalytic Oxidation of Carbon Monoxide at Room Temperature

Summary. The thermal and photoassisted catalytic oxidation of CO at metal oxide supported RuO₂·xH₂O was studied at room temperature. Contrary to neat RuO₂·xH₂O the supported catalysts suffer from fast deactivation attributed to strong adsorption of the reaction product carbon dioxide. The latter can be efficiently removed from the catalyst surface at elevated temperatures. In some cases, i.e. for catalysts supported with selected n-type semiconductors (TiO₂, SnO₂, WO₃), efficient CO₂ desorption and good, constant catalytic activity was observed upon visible light irradiation. Under such conditions the CO to CO₂ conversion observed for RuO₂·xH₂O/TiO₂ was nearly as good and stable as for the unsupported catalyst. It is suggested that light absorption promotes carbon dioxide desorption through positive charging of the catalyst surface.     

Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers

1 INTRODUCTION Ethers are a kind of organic compounds that are easily oxidized under the conditions of lacking light and any additional excitement. According to dif- ferent mechanisms, the oxidation reactions could be classified into two types: photooxidation reaction and dark oxidation reaction. The former is the reaction with excited state oxygen molecule (singlet state), while the latter is the reaction with ground state oxygen molecule (triple state) without illuminance or any exciter…     

Achievements,Challenges, and Perspectives on Nitrogen Electrochemistry for Carbon-Neutral Energy Technologies

Unrestrained anthropogenic activities have severely disrupted the global natural nitrogen cycle, causing numerous energy and environmental issues. Electrocatalytic nitrogen transformation is a feasible and promising strategy for achieving a sustainable nitrogen economy. Synergistically combining multiple nitrogen reactions can realize efficient renewable energy storage and conversion, restore the global nitrogen balance, and remediate environmental crises. Here, we provide a unique aspect to discuss the intriguing nitrogen electrochemistry by linking three essential nitrogen-containing compounds (i.e., N₂, NH₃, and NO₃⁻) and integrating four essential electrochemical reactions, i.e., the nitrogen reduction reaction (N₂RR), nitrogen oxidation reaction (N₂OR), nitrate reduction reaction (NO₃RR), and ammonia oxidation reaction (NH₃OR). This minireview also summarizes the acquired knowledge of rational catalyst design and underlying reaction mechanisms for these interlinked nitrogen reactions. We further underscore the associated clean energy technologies and a sustainable nitrogen-based economy.