Solid state NMR for dynamics and kinetics of hydrogen uptake and transport in novel bionanomaterials for energy applications ('Nano-NMR')

斯特恩报告强调，我们必须迅速转向使用可持续能源。进入氢经济还需要10-20年的时间。这主要受到四个方面的限制：(1)目前使用氢的燃料电池需要非常昂贵的贵金属电极和催化剂的寿命，以及高昂的费用，限制了燃料电池的经济性；（ii）需要更好的氢储存，以获得商业可行性所需的7%氢质量（金属氢化物储存太重了）；（iii）不仅贮藏中的氢质量，而且氢的摄取和释放动力学也至关重要；（iv）我们还没有技术来测量和跟踪固体基质中氢的形态和运输，或者，确实，有能力了解材料结构中发生的事情，因为它与氢相互作用。这项可行性研究汇集了两所大学的世界级专业知识，这些大学正在发展更密切的研究合作，以解决这些问题（在此之后的完整拨款提案成熟之前），在现有的学术和工业合作框架内，嵌入两项主要投资：DTI（630万美元用于基础设施）和EPSRC（150万美元用于使用现有材料的h -供应链研究）。这项可行性研究及其后续完整项目将在此框架内进行，与大约20家合作公司进行竞争，整个项目由伯明翰大学资助，由现任全职项目经理管理。在可行性研究中，我们将使用一种全新的方法：细菌生物制造贵金属纳米材料，自下而上，原子一个原子，失控的晶体生长和纳米颗粒团聚（这限制了商业合成）由细菌细胞表面的脚手架功能控制。这种生物纳米材料被认为有潜力优于商用燃料电池催化剂（2007年4月）；它们具有相当的活性（Bio-Pt）或完全意想不到的活性（Bio-Pd），生物制造具有高度可扩展到公斤/吨的规模。钯/金生物纳米杂化物最近得到了证实；这是目前燃料电池中“最先进的技术”，将Au(0)掺入双金属中，以原位氧化有毒的CO。我们将用生物金属和生物双金属混合物构建和测试PEM燃料电池，询问为什么这些燃料电池如此活跃（与商业材料相比），使用EPR、SQUID、XRD、FTIR和同步加速器方法作为工具，以及固体核磁共振（1H和2H）来跟踪金属晶格内的氢传输和形态形成。我们还将开始开发钯核本身的固态核磁共振，以获得对晶界/原位位错的Pd-H“对话”的新见解，这是迄今为止由于缺乏方法而无法达到的。氢存储的问题将通过采用潜在的轻质碳存储材料（活性炭颗粒和磨粉石墨；它们的h -动力学很差）来解决，并在它们上面覆盖一层钯薄膜。独特的是，Pd(0)能解离H2，并将氢作为高活性的自由氢原子移动。我们将利用细菌的能力在所有表面上定居和游动，甚至是闭塞的角落和缝隙。然后将细菌消毒并干燥，留下纳米pd(0)薄膜。这将结合Pd(0)优异的h转移和h传导特性（只需要几个原子厚度）和生物定向Pd膜（控制尺寸/分布）的能力，这对总体重量贡献很小。将H原子转移到Pd(0)/穿过Pd/C边界层并进入碳中，将使用固态1H和2H NMR来跟踪两种材料之间的“对话”，并确定当Pd(0)作为单个原子传递的H进入碳矩阵进行存储时发生了什么（以及有多快）。

The Stern report stresses that we must move rapidly to the use of sustainable energy. The move into the hydrogen economy is still 10-20 years away. This is desperately limited by four major issues: (i) current fuel cells that use hydrogen require precious metal electrodes which are very expensive and the catalyst life, and high expense, limit fuel cell economics; (ii) better hydrogen stores are needed to obtain the 7% H by mass needed for commercial viability (metal hydride based stores are simply too heavy); (iii) not only the H mass in the store, but also the kinetics of H uptake and release are vitally important; (iv) we do not yet have the technology to measure and follow the speciation and transport of hydrogen within solid matrices or, indeed, the capability to understand what is happening within the structure of the material as it interacts with hydrogen. This feasibility study brings together world class expertise across 2 universities that are developing closer research collaborations to address these problems (prior to maturation of a full grant proposal following this one) within an extant framework of academic and industrial collaboration, embedded within within two major investments: by the DTI (6.3m for infrastructure) and by EPSRC (1.5m for H-supply chain research using extant materials). This feasibility study, and its follow-up full project, will sit within this framework, against a raft of ~ 20 collaborating companies, the whole programme being managed by a full time project manager currently in post, funded by University of Birmingham. Within the feasibility study we will use a completely novel method: bacterial biomanufacturing of precious metal nanomaterials, bottom up, atom by atom, with runaway crystal growth and nanoparticle agglomeration (which limits commercial synthesis) controlled by the scaffolding function of the bacterial cell surface. Such bionanomaterials are suggested (April 07 Biotechnol Letts) to be potentially superior to commercial fuel cell catalysts; they are comparably active (Bio-Pt) or have totally unexpected activity (Bio-Pd) and biomanufacturing is highly scaleable to kilo/tonnage-scale. Pd/Au bionanohybrids are recently shown; this is current 'state of the art' in fuel cells where Au(0) is incorporated into bimetallics to oxidise poisonous CO in situ. We will construct and test PEM fuel cells with biometals and bio-bimetallic hybrids, asking WHY these are so active (versus commercial materials) using as tools EPR, SQUID, XRD, FTIR and synchrotron methods, as well as solid-sate NMR (1H and 2H) to follow specifically hydrogen transport and speciation within the metallic lattices. We will also start to develop solid state NMR of ther palladium nucleus itself, to gain novel insight into the Pd-H 'dialogue' at the grain boundaries/dislocations in situ which has beenbeyond reach until now by the lack of methodology. The problem of hydrogen stores will be tackled by adopting potential lightweight carbon storage materials (activated carbon particles and milled graphite; they have poor H-kinetics), overlaying these with a palladium thin film. Pd(0), uniquely, dissociates H2 and moves hydrogen around as highly reactive free H-atoms. We will use the ability of bacteria to colonise and swim over all surfaces, even occluded nooks and crannies. The bacteria will then be palladised and dried to leave a nano-Pd(0)-all-over-film. This will combine the excellent H-transfer and H-conduction properties of Pd(0) (only a few atoms thick is needed) with the ability to bio-direct a Pd-film (controlled size/distribution) which contrbutes little to the overall weight. Transfer of H atoms into the Pd(0)/across the Pd/C boundary layer and into the carbon, will be followed using solid state 1H and 2H NMR to follow the 'dialogue' between the two materials, and ascertain what is happening (and how fast) as the H delivered by the Pd(0) as individual atoms, goes into the carbon matrix for storage.