Hydrogen generation from liquid phase catalytic reforming of sugar solutions using metal-supported catalysts

Most of the hydrogen production processes are designed for large-scale industrial uses and are not suitable for a compact hydrogen device to be used in systems like solid polymer fuel cells. Integrating the reaction step, the gas purification and the heat supply can lead to small-scale hydrogen production systems. The aim of this research is to study the influence of several reaction parameters on hydrogen production using liquid phase reforming of sugar solution over Pt, Pd, and Ni supported on nanostructured supports. It was found that the desired catalytic pathway for H-2 production involves cleavage of C-C, C-H and O-H bonds that adsorb on the catalyst surface. Thus a good catalyst for production of H2 by liquid-phase reforming must facilitate C-C bond cleavage and promote removal of adsorbed CO species by the water-gas shift reaction, but the catalyst must not facilitate C-O bond cleavage and hydrogenation of CO or CO2. Apart from studying various catalysts, a commercial Pt/gamma-alumina catalyst was used to study the effect of temperature at three different temperatures of 458, 473 and 493 K. Some of the spent catalysts were characterised using TGA, SEM and XRD to study coke deposition. The amorphous and organised form of coke was found on the surface of the catalyst. (C) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Cobalt carbonate hydroxide nanowire array on ti mesh: an efficient and robust 3D catalyst for on-demand hydrogen generation from alkaline naBH4 solution.

In this work, for the first time, a cobalt carbonate hydroxide (Co(CO3 )0.5 (OH)⋅0.11 H2 O) nanowire array on Ti mesh (CHNA/Ti) was applied to drive the dehydrogenation of alkaline NaBH4 solution for on-demand hydrogen production. Compared with other nanostructured Co-based catalyst systems, CHNA/Ti can be activated more quickly and separated easily from fuel solutions. This self-supported cobalt salt nanowire array catalyst works as an efficient and robust 3D catalyst for the hydrolysis reaction of NaBH4 with a hydrogen generation rate of 4000 mL min(-1)  gCo (-1) and a low apparent activation energy of 39.78 kJ mol(-1) and offers an attractive system for on-demand hydrogen generation.

Photochemistry and chemometrics : an overview

Photochemistry has made significant contributions to our understanding of many important natural processes as well as the scientific discoveries of the man-made world. The measurements from such studies are often complex and may require advanced data interpretation with the use of multivariate or chemometrics methods. In general, such methods have been applied successfully for data display, classification, multivariate curve resolution and prediction in analytical chemistry, environmental chemistry, engineering, medical research and industry. However, in photochemistry, by comparison, applications of such multivariate approaches were found to be less frequent although a variety of methods have been used, especially with spectroscopic photochemical applications. The methods include Principal Component Analysis (PCA; data display), Partial Least Squares (PLS; prediction), Artificial Neural Networks (ANN; prediction) and several models for multivariate curve resolution related to Parallel Factor Analysis (PARAFAC; decomposition of complex responses). Applications of such methods are discussed in this overview and typical examples include photodegradation of herbicides, prediction of antibiotics in human fluids (fluorescence spectroscopy), non-destructive in- and on-line monitoring (near infrared spectroscopy) and fast-time resolution of spectroscopic signals from photochemical reactions. It is also quite clear from the literature that the scope of spectroscopic photochemistry was enhanced by the application of chemometrics. To highlight and encourage further applications of chemometrics in photochemistry, several additional chemometrics approaches are discussed using data collected by the authors. The use of a PCA biplot is illustrated with an analysis of a matrix containing data on the performance of photocatalysts developed for water splitting and hydrogen production. In addition, the applications of the Multi-Criteria Decision Making (MCDM) ranking methods and Fuzzy Clustering are demonstrated with an analysis of water quality data matrix. Other examples of topics include the application of simultaneous kinetic spectroscopic methods for prediction of pesticides, and the use of response fingerprinting approach for classification of medicinal preparations. In general, the overview endeavours to emphasise the advantages of chemometrics' interpretation of multivariate photochemical data, and an Appendix of references and summaries of common and less usual chemometrics methods noted in this work, is provided. Crown Copyright © 2010.

The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

Synthesis of nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) solid solution exhibiting high CO oxidation and water gas shift activity

Nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) has been synthesized using a low temperature sonication method and characterized using XRD, TEM, XPS and H-2-TPR. The potential application of both the solid solutions has been explored as exhaust catalysts by performing CO oxidation. The addition of Si- and Fe-in Ce0.95Ru0.05O2-delta greatly enhanced the reducibility of Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe), as indicated by the H-2-TPR study. The oxygen storage capacity has been used to correlate surface oxygen reactivity to the CO oxidation activity. Both the compounds reversibly release lattice oxygen and exhibit excellent CO oxidation activity with 99% conversion below 200 degrees C. A bifunctional reaction mechanism involving CO oxidation by the extraction of lattice oxygen and rejuvenation of oxide vacancy with gas feed O-2 has been used to correlate experimental data. The performance of both the solid solutions has also been investigated for energy application by performing the water gas shift reaction. The present catalysts are highly active and selective towards the hydrogen production and a lack of methanation activity is an important finding of present study.

Catalytic performance of highly dispersed Ni/TiO2 for dry and steam reforming of methane

The present study reports a sonochemical-assisted synthesis of a highly active and coke resistant Ni/TiO2 catalyst for dry and steam reforming of methane. The catalyst was characterized using XRD, TEM, XPS, BET analyzer and TGA/DTA techniques. The TEM analysis showed that Ni nanoparticles were uniformly dispersed on TiO2 surface with a narrow size distribution. The catalyst prepared via this approach exhibited excellent activity and stability for both the reactions compared to the reference catalyst prepared from the conventional wet impregnation method. For dry reforming, 86% CH4 conversion and 84% CO2 conversion was obtained at 700 degrees C. Nearly 92% CH4 conversion and 77% CO selectivity was observed under a H2O/CH4 ratio of 1.2 at 700 degrees C for the steam reforming reaction. In particular, the present catalyst is extremely active and resistant to coke formation for steam reforming at low steam/carbon ratios. There is no significant modification of Ni particles size and no coke deposition, even after a long term reaction, demonstrating its potential applicability as an industrial reformate for hydrogen production. The detailed kinetic studies have been presented for steam reforming and the mechanism involving Langmuir-Hinshelwood kinetics with adsorptive dissociation of CH4 as a rate determining step has been used to correlate the experimental data.

Catalisadores à base de platina frente a correntes de H2 contendo acetaldeído geradas via reforma do etanol

Devido ao efeito estufa, a produção de hidrogênio a partir da reação de reforma do bioetanol tem se tornado um assunto de grande interesse em catálise heterogênea. Os catalisadores à base de Pt são empregados nos processos de purificação de H2 e também em eletrocatalisadores das células a combustível do tipo membrana polimérica (PEMFC). O hidrogênio obtido a partir da reforma do etanol contém como contaminante o acetaldeído e pequenas quantidades de CO. Assim, pode-se prever que muitas reações podem ocorrer na presença de catalisadores de Pt durante o processo de purificação do H2 e mesmo no próprio eletrocatalisador. Desta forma, este trabalho tem como objetivo descrever o comportamento do acetaldeído na presença de catalisadores de Pt. Para tanto foram preparados dois catalisadores, Pt/SiO2 e Pt/USY, contendo 1,5% de metal em ambos. Também foi estudado um eletrocatalisador (comercial) de Pt suportado em carvão (Pt/C). Os catalisadores foram caracterizados através das técnicas de análise textural, difração de raios X (DRX), quimissorção de H2, reação de desidrogenação do ciclohexano, espectroscopia no infravermelho de piridina adsorvida, dessorção a temperatura programada de n-butilamina (TPD de n-butilamina), dessorção a temperatura programada de CO2 (TPD-CO2), análise termogravimétrica, microscopia eletrônica de varredura (MEV) e espectroscopia de dispersão de energia (EDS). Os testes catalíticos foram realizados entre as temperaturas de 50 e 350 C em corrente contendo acetaldeído, H2 e N2. Foi observado que as propriedades ácido-básicas dos suportes promovem as reações de condensação com formação de éter etílico e acetato de etila. O acetaldeído em catalisadores de Pt sofre quebra das ligações C-C e C=O. A primeira ocorre em uma ampla faixa de temperaturas, enquanto a segunda apenas em temperaturas abaixo de 200 C. A quebra da ligação C-C produz metano e CO. Já a quebra da ligação C=O gera carbono residual nos catalisadores, assim como espécies oxigênio, que por sua vez são capazes de eliminar o CO da superfície dos catalisadores. Nota-se que o tipo de suporte utilizado influencia na distribuição de produtos, principalmente a baixas temperaturas. Além disso, constatou-se que a descarbonilação não é uma reação sensível à estrutura do catalisador. Verificou-se também a presença de resíduos sobre os catalisadores, possivelmente oriundos não somente da quebra da ligação C=O, mas também de reações de polimerização

Generación combinada a partir de biogás de calor y electricidad

[ES]El análisis y la resolución de casos prácticos engloban la resolución de casos prácticos, el análisis de las alternativas posibles o la resolución de casos concretos. En este trabajo se pretende analizar y resolver un caso concreto, de un proceso de producción de hidrógeno. Una vez expuesto el contexto y el análisis de las alternativas, se procederá a explicar el proceso de obtención y aprovechamiento del hidrógeno. El hidrógeno, se obtendrá a partir de la gasificación d la biomasa. Una vez se haya obtenido la corriente de hidrógeno, esta alimentará a una pila de alta temperatura tipo SOFC, para obtener generación combinada de calor y electricidad.

微藻光合放氢的生理生化调控及生物技术研究

氢能将是主宰未来世界的主要能源之一，氢能的研究开发已经成为世界各国能源研究的重要方向。微藻光合制氢，因其无污染、可再生，成为生物制氢领域最有应用前景的研究方向之一。 本论文选取模式植物莱茵衣藻、经济藻种钝顶螺旋藻作为实验材料，对微藻光合放氢的生理生化过程调控及相关生物技术进行综合研究。获得的主要成果如下： （1）建立起微藻两步法放氢的技术平台和批次培养的回馈监控模式;同时，运用离子色谱追踪整个放氢过程中的离子变化，我们的实验结果证明对于衣藻两步法放氢而言，乙酸的存在是必要条件之一。这个结果与文献报道不尽相同，值得进一步深入地研究。 （2）筛选出一株联合固氮菌，摸索出藻菌共培养的培养基合适配置和活性控制条件;在两步法放氢的基础上，充分利用藻菌之间的优势互补，设计构建藻菌共培养放氢体系，与两步法放氢比较，该体系能提前12小时进入放氢状态，提高单位叶绿素放氢效率1倍左右，延长体系稳定时间近20小时。 （3）利用固定化技术获得高产氢效率，去固定化后持续产氢是我们设计出微藻连续放氢的一个特点。同时，摸索出衣藻放氢过程中的间歇进料进流程序，使连续放氢时间可达3周左右。 （4）实验证明两步法放氢技术，并不适用于螺旋藻;同时，在摸索建立螺旋藻的藻菌共培养放氢体系过程中，发现非致病性肺炎克雷伯氏杆菌培养液可以破碎螺旋藻细胞，这种全新的提取藻蓝蛋白的方法，具有节约成本，便于操作，温和均匀的独特优势。 （5）在连续放氢体系中加入适量蔗糖做底物和引物，剩余存活的菌可以继续利用提取藻蓝蛋白后剩余螺旋藻藻渣和放氢后死亡的衣藻进行发酵放氢，可获得更高产率的氢气，之后继续利用光合细菌进一步放氢，形成连续放氢网络，这一步还在探索之中。 作为一项应用基础研究，从三角瓶里的实验到工厂化生产还有很长的路，希望本实验的工作能为以后同类研究提供一些有用的信息和启发。

Design of Narrow-Gap TiO2: A Passivated Codoping Approach for Enhanced Photoelectrochemical Activity

To improve the photoelectrochemical activity of TiO2 for hydrogen production through water splitting, the band edges of TiO2 should be tailored to match with visible light absorption and the hydrogen or oxygen production levels. By analyzing the band structure of TiO2 and the chemical potentials of the dopants, we propose that the band edges of TiO2 can be modified by passivated codopants such as (Mo+C) to shift the valence band edge up significantly, while leaving the conduction band edge almost unchanged, thus satisfying the stringent requirements. The design principle for the band-edge modification should be applicable to other wide-band-gap semiconductors.

The role of CeO2-ZrO2 as support in the ZnO-ZnCr2O4 catalysts for autothermal reforming of methanol

Autothermal reforming of methanol for hydrogen production was investigated over ZnO-ZnCr2O4 supported on a series of metal oxides (Al2O3, CeO2, ZrO2 and CeO2-ZrO2)CeO2-ZrO2 mixed oxides with Ce /Zr molar ratio of 4/1 was found to be the optimal support which showed significant effect on the catalytic activity and selectivity. The ZnO-ZnCr2O4/CeO2-ZrO2 and ZnO-ZnCr2O4 catalysts were characterized by XRD, TEM, H-2-TPR and XPS. The results show that CeO2-ZrO2 mixed oxides have significant effect on the catalytic performance and the supported catalyst shows more uniform temperature distribution in the catalyst bed which was mainly due to its reasonable redox properties.