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。进入氢气经济还需要10到20年的时间。这受到四个主要问题的严重限制：(I)目前使用氢的燃料电池需要非常昂贵的贵金属电极，催化剂的寿命和高昂的费用限制了燃料电池的经济性；(Ii)需要更好的氢气存储来获得商业生存所需的7%的质量H(基于金属氢化物的存储实在太重了)；(Iii)不仅存储中的H质量，而且吸氢和释放氢的动力学也至关重要；(4)我们还没有技术来测量和跟踪氢在固体基质中的形态和传输，或者确实没有能力了解在材料与氢相互作用时在其结构内发生了什么。这项可行性研究汇集了两所大学的世界级专业知识，这两所大学正在开展更密切的研究合作，以在现有的学术和产业合作框架内解决这些问题(在随后的全面拨款提案成熟之前)，并嵌入两项主要投资：DTI(630万用于基础设施)和EPSRC(150万用于利用现有材料进行H-供应链研究)。这项可行性研究及其后续的完整项目将在这一框架内进行，面对一批约20家合作公司，整个项目由伯明翰大学资助的一名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：由细菌细胞表面的支架功能控制细菌生物制造贵金属纳米材料，自下而上，一个原子一个原子地控制晶体生长和纳米粒子团聚(这限制了商业合成)。这类生物材料被认为可能优于商业燃料电池催化剂；它们具有类似的活性(Bio-铂)或完全意想不到的活性(Bio-Pd)，并且生物制造可高度扩展到千吨级。最近展示了Pd/Au生物阳极杂化材料；这是燃料电池的当前‘最先进的状态’，其中Au(0)被结合到双金属化合物中，以原位氧化有毒的CO。我们将使用生物金属和生物双金属杂化材料构建和测试PEM燃料电池，使用EPR、SQUID、X射线衍射、FTIR和同步加速器方法以及固体核磁共振(1H和2H)作为工具来研究为什么这些燃料电池如此活跃(与商业材料相比)，以跟踪金属晶格中的氢传输和物种形成。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/位错处的Pd-H‘对话’的新见解，这是到目前为止由于缺乏方法学而达不到的。氢储存的问题将通过采用潜在的轻质碳储存材料(活性碳颗粒和研磨石墨；它们的氢动力学很差)来解决，在它们上面覆盖一层钯薄膜。独一无二的是，Pd(0)解离H2，并以高活性的自由H原子的形式移动氢气。我们将利用细菌在所有表面定居和游动的能力，甚至是被遮挡的角落和缝隙。然后，细菌将被苍白和干燥，留下一层纳米Pd(0)-All-Over膜。这将结合Pd(0)的优良的氢转移和氢传导特性(只需要几个原子厚度)和生物定向Pd膜的能力(控制尺寸/分布)，这对总重量的影响很小。氢原子转移到Pd(0)/穿过Pd/C边界层并进入碳，随后将使用固态1H和2H核磁共振跟踪两种材料之间的‘对话’，并确定发生了什么(以及多快)，因为由Pd(0)作为单个原子提供的H进入碳基质进行存储。

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 the palladium nucleus itself, to gain novel insight into the Pd-H 'dialogue' at the grain boundaries/dislocations in situ which has been beyond 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.