Nanoporous Palladium Hydride for Electrocatalytic N2 Reduction under Ambient Conditions

The electrocatalytic nitrogen reduction reaction (NRR) is an alternative eco‐friendly strategy for sustainable N₂ fixation with renewable energy. However, NRR suffers from sluggish kinetics owing to difficult N₂ adsorption and N≡N cleavage. Now, nanoporous palladium hydride is reported as electrocatalyst for electrochemical N₂ reduction under ambient conditions, achieving a high ammonia yield rate of 20.4 μg h^?1 mg^?1 with a Faradaic efficiency of 43.6 % at low overpotential of 150 mV. Isotopic hydrogen labeling studies suggest the involvement of lattice hydrogen atoms in the hydride as active hydrogen source. In situ Raman analysis and density functional theory (DFT) calculations further reveal the reduction of energy barrier for the rate‐limiting *N₂H formation step. The unique protonation mode of palladium hydride would provide a new insight on designing efficient and robust electrocatalysts for nitrogen fixation.     

Hydride Formation Diminishes CO2 Reduction Rate on Palladium

The catalytic hydrogenation of CO₂ includes the dissociation of hydrogen and further reaction with CO₂ and intermediates. We investigate how the amount of hydrogen in the bulk of the catalyst affects the hydrogenation reaction taking place at the surface. For this, we developed an experimental setup described herein, based on a magnetic suspension balance and an infrared spectrometer, and measured pressure-composition isotherms of the Pd−H system under conditions relevant for CO₂ reduction. The addition of CO₂ has no influence on the measured hydrogen absorption isotherms. The pressure dependence of the CO formation rate changes suddenly upon formation of the β-PdH phase. This effect is attributed to a smaller surface coverage of hydrogen due to repulsive electronic interactions affecting both bulk and surface hydrogen.     

Peculiarities of Morphology of Tin Microcrystals Electroplated under Galvanostatic Conditions

Russian Journal of Electrochemistry - Specific features of morphology of structure of tin microcrystals, which form during the electrodeposition under the galvanostatic conditions on the...     

硒、碲氢化物发生的反应机理和反应条件

元素周期表中ⅣA,ⅤA及ⅥA族元素的化学及物理性质的周期性变化引起硒、碲两元素的氢化物生成反应机理的改变。文中对两元素生成氢化物的反应机理作了解释,认为是硒(Ⅳ)[或碲(Ⅳ)]在盐酸溶液中与初生态氢[H]反应的结果。初生态氢是由硼氢根(BH4-)在酸溶液中水解而产生,反应时随氢离子(即酸度)浓度的增加,氢化物的生成率将明显提高。此外,不断地将氢化物发生反应中同时生成的水蒸气除去不仅可避免硒(碲)氢化物被氧化,而且还可提高其产出率和峰值测定的重现性。对如何规范使用低熔点、高强度空心双阴极灯也作了评价。     

Disperse Electrolytic Platinum and Palladium Deposits of Submicron Thickness on Polycrystalline Supports: An X-ray Diffractometry and Microscopy Study

The structure of model electrode materials broadly used in electrocatalysis (platinized platinum, palladized platinum, platinized gold) is studied by x-ray diffractometry, scanning electron microscopy, and transmission electron microscopy. Disperse platinum and palladium coatings less than 1 m thick are obtained by potentiostatic or galvanostatic deposition from solutions of complex chloride salts. Lattice parameters of disperse metals are shown to be considerably smaller than those of bulky crystals. Some new tendencies of variations in structural parameters with the deposition potential are revealed. Special attention is paid to a reliable determination of the size of regions of coherent scattering (ROCS) and microdistortion; in connection with this, results of approximation of reflections by various functions and a harmonic analysis of reflections are compared. The latter are used for constructing ROCS distributions by size. Good agreement is found with the STM data for platinum deposits obtained earlier. Conversely, in the case of palladium deposits, ROCS are smaller than the particle size in an outer layer of the deposit by the STM data. This result is interpreted in terms of strong concrescence of palladium nanoparticles. To determine the true surface areas of deposits and estimate continuousness of covering the support by the deposit and regularities of platinum aging on gold in conditions of potential cycling, a voltammetry method is applied.     

钯催化下活性亚甲基化合物的烯丙基化相转移反应

钯催化下活性亚甲基化合物的烯丙基化反应在有机合成中是一种十分有用的方法。例如在双三苯基膦二氯化钯催化下丙二酸二乙酯、α-砜基乙酸乙酯等活性亚甲基化     

E-selective Semi-hydrogenation of Alkynes under Mild Conditions by a Diruthenium Hydride Complex

The synthesis, characterization and catalytic activity of a new class of diruthenium hydrido carbonyl complexes bound to the ^{t Bu} PNNP expanded pincer ligand is described. Reacting ^{t Bu} PNNP with two equiv of RuHCl(PPh₃)₃(CO) at 140 °C produces an insoluble air-stable complex, which was structurally characterized as [Ru₂(^tBuPNNP)H(μ-H)Cl(μ-Cl)(CO)₂] ( 1 ) using solid-state NMR, IR and X-ray absorption spectroscopies and follow-up reactivity. A reaction with KOtBu results in deprotonation of a methylene linker to produce [Ru₂(^tBuPNNP^*)H(μ-H)(μ-OtBu)(CO)₂] ( 3 ) featuring a partially dearomatized naphthyridine core. This enables metal-ligand cooperative activation of H₂ analogous to the mononuclear analogue, [Ru(^tBuPNP*)H(CO)]. In contrast to the mononuclear system, the bimetallic analogue 3 catalyzes the E-selective semi-hydrogenation of alkynes at ambient temperature and atmospheric H₂ pressure with good functional group tolerance. Monitoring the semi-hydrogenation of diphenylacetylene by ¹H NMR spectroscopy shows the intermediacy of Z-stilbene, which is subsequently isomerized to the E-isomer. Initial findings into the mode of action of this system are provided, including the spectroscopic characterization of a polyhydride intermediate and the isolation of a deactivated species with a partially hydrogenated naphthyridine backbone.     

Formation of Anisotropic Hydroxyapatite Particles under Hydrothermal Conditions

Russian Journal of Applied Chemistry - Using X-ray diffraction analysis, transmission electron microscopy, and complex thermal analysis, it was shown that brushite crystals are formed from aqueous...     

Carbonylation of Olefins under Mild Temperature Conditions in the Presence of Palladium Complexes

During a search for catalysts that allow carbonylation reactions on olefins to proceed below 100 °C, complex palladium(II ) compounds having the formula L_mPdX_n were found to be catalytically active. L denotes a ligand such as a phosphine, nitrile, amine, or olefin, X is an acid residue, and m+n is 3 or 4. The catalysts permit the carbonylation of heat-sensitive compounds, as well as selective carbonylation of polyunsaturated olefins. The new process can also be carried out on the industrial scale, as is shown by the carbonylation of cyclododecatriene     

Catalytic Synthesis of Aluminum Hydride in the Presence of Palladium Black

The catalytic properties of a palladium catalyst in the formation of aluminum hydride are studied. The formation of stoichiometric aluminum hydride is determined by XRD, DTA, and spectrophotometry. Findings are rationalized in terms of the electron-chemical catalytic scheme.     

Palladium Mediated Formation of Bithiophenes

The palladium-catalyzed coupling of iodothiophenes and stannylthiophenes gave good yields of bithiophene derivatives. This versatile reaction is tolerant of numerous functional groups.     

Assessment of Phase Composition of Electrolytic Deposits by Stripping Voltammetry

This paper describes the method of assessing the composition of the intermetallic compounds in nanoscale electrolytic deposits. The formula was developed for calculating the deflection potential in the case of selective electrooxidation electronegative component of the alloy composition. The processes of electro binary electrolytic precipitation in mercury-rhodium chloride electrolyte by anodic stripping voltammetry were studied. It was established that an electrolytic precipitate contains rhodium, mercury and rhodium IC with mercury composition Hg₅Rh.     

原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究

利用~1H-NMR原位追踪在L-缬氨酸存在下合成花状纳米聚苯胺的形成过程中发现此结构的形成经历3个阶段:首先在苯胺与缬氨酸构成的类胶束结构内聚合成吩嗪类寡聚物;其次通过p-p重叠作用及胶束融合过程成为片状聚集体;最终通过与缬氨酸形成氢键组装成花瓣状纳米聚苯胺.通过改变反应条件,对比形成过程中核磁共振图谱及产物形貌的变化发现花状纳米聚苯胺的形成有如下特征:反应初期L-缬氨酸作为缓冲试剂可以避免苯胺的骤然质子化,有利于生成具有吩嗪结构的寡聚物;反应前苯胺单体与缬氨酸形成稳定的反应环境保证寡聚物始终在其内聚集生长,有效避免了外部环境的影响.     

Radical Formation in Sugar-Derived Acetals under Solvent-Free Conditions

The degradation of acetal derivatives of the diethylester of galactarate (GalX) was investigated by electron paramagnetic resonance (EPR) spectroscopy in the context of solvent-free, high-temperature reactions like polycondensations. It was demonstrated that less substituted cyclic acetals are prone to undergo radical degradation at higher temperatures as a result of hydrogen abstraction. The EPR observations were supported by the synthesis of GalX based polyamides via ester-amide exchange-type polycondensations in solvent-free conditions at high temperatures in the presence and in the absence of radical inhibitors. The radical degradation can be offset by the addition of a radical inhibitor. The radical is probably formed on the methylene unit between the oxygen atoms and subsequently undergoes a rearrangement.     

水合物生成条件下甲烷在水中的吸附

采用悬滴法系统地测定了温度274.2 ~ 282.2 K、压力0.1 ~ 10.1 MPa下甲烷/纯水间界面张力。实验结果表明在恒定温度下界面张力随压力的增加而增大。在高压条件下,压力对界面张力有很大的影响。不同温度和压力下计算出的甲烷在水中的表面过剩浓度结果表明,压力越高,温度越低,甲烷在水溶液中的吸附浓度越高。同时,计算出的甲烷在水溶液中的表面吸附自由能结果表明,在水合物生成条件下,甲烷在水中的吸附比298.2 K更容易。     

氢化钛的制备及其分解

钛是具有吸氢作用的金属元素之一，用于制备超纯氢气“’“，但纯金属钛作为储氢材料却一直认为没有实用价值“‘．近年来对钛与氢作用引起的微观缺陷及钛的氢化物结构和形成机制等方面进行了一些研究［‘，’j，但并未解决钛与氢作用的实用性问题．本文对在常压下钛与氢气的化学反应、所生成氢化物的结构形态，及分解释放氢气的条件和热力学关系进行了研究．取海绵钛颗粒于石墨舟中，然后将石墨舟推入430X2mm的1．5m长石英反应管，该反应管置于管式炉中．在持续氢气流中缓慢加热升温，随时调节氢气流量，以维持系统恒压，并在35OC恒温3Om…     

Hierarchically Organized Silica–Titania Monoliths Prepared under Purely Aqueous Conditions

Hierarchically organized silica–titania monoliths were synthesized under purely aqueous conditions by applying a new ethylene glycol‐modified single‐source precursor, such as 3‐[3‐{tris(2‐hydroxyethoxy)silyl}propyl]acetylacetone coordinated to a titanium center. The influence of the silicon‐ and titanium‐containing single‐source precursor, the novel glycolated organofunctional silane, and the addition of tetrakis(2‐hydroxyethyl)orthosilicate on the formation of the final porous network was investigated by SEM, TEM, nitrogen sorption, and SAXS/WAXS. In situ SAXS measurements were performed to obtain insight into the development of the mesoporous network during sol–gel transition. IR‐ATR, UV/Vis, XPS, and XAFS measurements showed that up to a Si/Ti ratio of 35:1, well‐dispersed titanium centers in a macro‐/mesoporous SiO₂ network with a specific surface area of up to 582 m² g^?1 were obtained. An increase in Ti content resulted in a decrease in specific surface area and a loss of the cellular character of the macroporous network. With a 1:1 Si/Ti ratio, silica–titania powders with circa 100 m² g^?1 and anatase domains within the SiO₂ matrix were obtained.