Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.     

Ultrasmall rhodium nanoclusters anchored on nitrogen-doped carbon nanotubes with embedded nickel nanoparticles as magnetically recyclable catalysts for efficient ammonia-borane hydrolysis

Facile yet efficient synthesis of high-performance nanocatalysts for hydrogen evolution from ammonia-borane (AB) hydrolysis is paramount. Here, we reported a novel hybrid nanocatalyst comprised of Rh nanoclusters (1.56 nm in diameters) anchored on nitrogen (N)-doped carbon nanotubes with embedded Ni nanoparticles (Ni@NCNTs), which was fabricated through adsorption of Rh ions on Ni@NCNTs. The achieved hybrid of Rh/Ni@NCNTs displayed excellent catalytic property (Turnover frequency: 959 min⁻¹) toward AB hydrolysis, higher than many prior developed Rh-based catalysts. Note that this hybrid could be reused for at least nine runs with complete AB conversion to hydrogen. Rh nanoclusters with small size exhibiting high atom utilization and the synergetic effect between Ni and Rh are responsible for the excellent catalytic property of Rh/Ni@NCNTs toward AB hydrolysis. This work highlights the importance of utilization of magnetically recyclable Ni@NCNTs as support and synergetic component for efficient hydrolysis of AB.     

Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

An effective rhodium catalyst system on the synthesis of acetic acid from methyl formate

Rh/Lil/SnR₄ is an effective catalyst system for the conversion of methyl formate to acetic acid under carbon monoxide pressure. The effects of solvent and initial CO partial pressure on the turnover rate of the reaction were investigated. The possibility of replacing some of the iodide promoters by tin compounds has been probed.     

Structural and surface properties of thermally prepared Ti/RhxTi(1−x)Oy electrodes: I—influence of preparation parameters

Electrodes of Rh_xTi_(1−x)O_y nominal composition were prepared by thermal decomposition of the chloride or nitrate precursor salts dissolved in strongly acidic medium and applied by brush to both sides of a Ti° support. A systematic study of the influence of calcination temperature and time as well as oxygen flux was conducted. The coatings were characterised by SEM, EDAX, XRD, open circuit potential measurements and cyclic voltammetry (CV). Visible-ultraviolet spectrophotometry was employed to identify the chemical form of the precursor in solution while thermogravimetric analysis (TGA) was used to assess the decomposition temperature ranges. Optimisation of the coating preparation parameters showed coatings obtained from [Rh(H₂O)₆](NO₃)₃ precursor dissolved in HNO₃ 1:2 (v/v) and fired at 430 °C for 2 h in a 5 l min⁻¹ oxygen stream-furnished stable electrodes having the highest electrochemically active surface area.     

Syngas production by biomass gasification using Rh/CeO2/SiO2 catalysts and fluidized bed reactor

We have been developed novel catalysts for gasification of biomass with much higher energy efficiency than conventional methods (non-catalyst, dolomite, commercial steam reforming Ni catalyst). From the result of the gasification of cellulose over novel Rh/CeO₂/SiO₂ catalysts, it is found that the gasification process consists of the reforming of tar and the combustion of solid carbon. We also tested novel Rh/CeO₂/SiO₂ in the gasification with air, pyrogasification, and steam reforming of cedar wood. As a result, Rh/CeO₂/SiO₂ gave higher yield of syngas than the conventional steam reforming Ni catalyst. Furthermore, we compared the performance between single and dual bed reactors. Single bed reactor was effective in the gasification of cedar, however, it was not suitable for the gasification of rice straw since a rapid deactivation was observed. Gasification of rice straw, jute stick, baggase using the fluidized dual-bed reactor and Rh/CeO₂/SiO₂ was also investigated. Especially, the catalyst stability in the gasification of rice straw clearly was enhanced by using the fluidized dual bed reactor.     

ICP－AES法对Pt－Pd－Rh－RE合金中各组分的同时测定

研究了ＩＣＰ─ＡＥＳ法对ＰｔＰｄＲｈ、ＰｔＰｄＲｈＣｅ、ＰｔＰｄＲｈＹ合金中Ｐｄ、Ｒｈ、Ｃｅ、Ｙ的同时测定方法。通过对同一样品不同测定方法对照，认为本方法简便、快速、适用性广。本法测定的范围是；Ｃｃ、Ｙ０．１～１％；Ｒｈ０．６～６％；Ｐｄ２～２０％。相对误差最大为２％，变差系数＜１％。     

铑与DBS—偶氮氯膦的新显色反应

研究了Rh与DBS—偶氮氯膦的显色反应。在Na_2HPO_4—H_3PO_4缓冲介质中,当抗坏血酸存在并加热的条件下可生成蓝色配合物。Rh含量在0～22μg/25ml符合比尔定律,ε_(620)=1.25×10~4。此方法用于Rh—Ir回收液中Rh的测定,结果满意。     

从废铑催化剂中提取铑粉

介绍了从大庆石化总厂丁辛醇生产装置排出的废铑催化剂回收Rh的工艺流程及其生产方法，包括焚烧、溶解、电解回收、酸洗、焙烧等工序，该回收工艺简单，成本低，Rh总回收率＞95％，所得Rh纯度＞99.5%。     

Rh(Ⅲ)—钍试剂—高碘酸钾新体系催化光度法测定痕量铑

在pH3.9醋酸盐缓冲溶液中及加热条件下,Rh(Ⅲ)对高碘酸钾氧化钍试剂这一褪色反应有强烈的催化作用,可藉自来水冷却中止反应,研究了催化光度测定痕量铑的影响因素,建立了一个检出限和测定范围分别为0.06ng/ml和0.12～4.5ng/ml铑的催化光度新方法。