EPRI: Collaborative Research: Hydrogen Production via Electrochemical Reforming of Ethanol in a Proton Exchange Membrane Cell

已经提出从生物质和/或生物燃料生产氢作为当前从化石燃料（例如甲烷和煤）生产氢与使用可再生源（例如，太阳能和风能）。 本项目旨在开发一种高能效的质子交换膜（PEM）电池中通过乙醇电化学重整反应（EER）制氢的工艺。 乙醇是一种有吸引力的氢生产原料，因为现有的基础设施，其大规模生产的生物质。本研究将探索使用部分氧化的贵金属催化剂作为一组新的阳极催化剂，实现快速反应动力学（快速电荷转移）和高效率。将在PEM电池中研究通过EER过程生产氢气，其中析氢反应发生在阴极，限速乙醇氧化反应发生在阳极。 假设是：（1）部分氧化的贵金属（MOx）晶格氧比吸附的OH（水在电催化中作为常见氧化剂的解离产物）更能有效地去除有毒物种;（2）与贵金属（M）和O组分的特定排列相关的系综效应可能对乙醇的C-C裂解起重要作用。 将通过理论和实验研究相结合来测试假设：将进行密度泛函理论（DFT）计算，以研究板状和纳米颗粒形式的部分氧化贵金属（MOx，M：Pt，Rh，Ir，Pd和Ru）的稳定性和对C-C分裂的反应性。溶液相合成的MOx簇，预测由DFT计算具有高效率的乙醇完全氧化，将进行。将使用各种技术，包括像差校正扫描透射电子显微镜和X射线吸收光谱（XAS）在国家实验室的集群的结构表征。 EER动力学将在半电池和单电池中进行评估，从中计算能量效率，氢气和二氧化碳生成速率以及选择性，并用于评估所提出的MOx催化剂的性能。

Production of hydrogen from biomass and/or biofuels has been proposed as an interim method between the current hydrogen production from fossil fuels, such as methane and coal, and hydrogen production using renewable sources (e.g., solar and wind). This project aims to develop a highly energy-efficient process for hydrogen production in a proton exchange membrane (PEM) cell via the ethanol electrochemical reforming reaction (EER). Ethanol is an attractive feedstock for hydrogen production because of the existing infrastructure for its large-scale production from biomass. The proposed work will investigate the use of partially oxidized noble metal catalysts as a new group of anode catalysts enabling fast reaction kinetics (rapid charge transfer) and high efficiency.The production of hydrogen by the EER process will be studied in a PEM cell, where the hydrogen evolution reaction happens at the cathode and the rate-limiting ethanol oxidation reaction happens at the anode. The hypotheses are: (1) Lattice oxygen from partially oxidized noble metals (MOx) will be more active to remove poisoning species than adsorbed OH (the dissociative product of water acting as a common oxidant in electro-catalysis); (2) The ensemble effect, associated with particular arrangements of the noble metal (M) and O constituents, may play an important role towards the C-C splitting of ethanol. The hypotheses will be tested by a combination of theoretical and experimental investigations: Density functional theory (DFT) calculations will be performed to study the stability and reactivity towards C-C splitting on partially oxidized noble metals (MOx, M: Pt, Rh, Ir, Pd and Ru) in slab and nanoparticle forms. Solution phase synthesis of MOx clusters, predicted by DFT calculations to have high effectiveness for complete oxidation of ethanol, will be performed. Structural characterization of the clusters will be performed using a variety of techniques, including aberration-corrected scanning transmission electronic microscopy and X-ray absorption spectroscopy (XAS) at National Laboratories. EER kinetics will be evaluated in both half-cells and single-cells, from which energy efficiency, hydrogen and carbon dioxide generation rates, and selectivity will be calculated and used to evaluate the performance of the proposed MOx catalysts.