Spectroscopy-driven design of an efficient photocatalyst for CO2 reduction (Ext.)

这是原来的奖学金“光谱驱动的设计一个有效的光催化剂减少二氧化碳“有足够的太阳能入射到英国，以提供我们所有的能源需求。然而，日照水平在一天之内和季节性水平上变化很大。任何能源技术要想可行，就必须可靠。克服供应问题的一个途径是使用太阳能来驱动化学燃料的生产，该化学燃料可以存储和运输，以便在需要的时候和地方使用。可持续的碳基太阳能燃料和原料（例如CH 4、CH 3OH、CO）可以通过光驱动的水氧化与CO2还原的耦合来生产。这是一个令人兴奋的前景，但要实现低碳强度燃料经济性的目标，燃料生产和利用系统都需要突破。目前用于CO2还原和水氧化的材料不能以可行的成本实现所需的效率和稳定性水平。同样，最有前途的清洁发电技术，从碳燃料，燃料电池，通常遭受相对较低的效率和对燃料进料中杂质的不耐受性。最初的奖学金在提供新的低成本催化剂方面非常成功，这些催化剂可以直接由阳光驱动光催化剂）或间接使用电能（原则上可来自PV板）将CO2还原为CO（一种重要的液体燃料前体）。最初的奖学金的一部分在英国开发了高灵敏度表面灵敏光谱学的新能力，IR-Vis和频发生光谱学。该实验已被用于以令人难以置信的细节水平识别表面催化剂的机制。这些，以及我们更广泛的光谱研究，在指导我们自己的催化剂设计方案中至关重要。但是，对机械论见解的需要超出了我们自己的合成程序。对电极和光电极表面上发生的催化机制缺乏了解是整个领域的限制因素，阻碍了新材料的合理开发。因此，我们的光谱驱动计划将扩大到解决燃料生成的关键反应（水氧化和CO2还原）以及燃料利用化学，通过研究最先进的金属氧化物燃料电池。该项目是雄心勃勃的，其目标不仅是在最常研究的光电极（赤铁矿）上首次鉴定水氧化过程中的所有关键中间体，而且还探索与水和电解质盐的次级相互作用如何控制活性。从领先的CO2还原催化剂和燃料电池电极中也可以找到类似水平的机理细节。我们旨在提供的这种机械细节水平可能会对我们自己、合作者和更广泛的社区物质发展计划产生变革性影响。为太阳能燃料的生产和利用提供可扩展的高效材料是一个具有挑战性的目标，但潜在的影响是巨大的。更好地理解当前材料的表面机制将是实现这一目标的重要一步。

This is an extension of the original Fellowship "Spectroscopy-driven design of an efficient photocatalyst for CO2 reduction"There is sufficient solar energy incident on the UK to provide for all of our energy needs. However the insolation level varies hugely both within a day and on a seasonal level. For any energy technology to be viable it is essential that it is reliable. A route to overcoming the intermittency of supply issue is to use the solar energy to drive the production of a chemical fuel which can be stored and transported to be available when and where it is needed. Sustainable carbon-based solar fuels and feedstocks (e.g. CH4, CH3OH, CO) can be produced by the coupling of light driven water oxidation to the reduction of CO2. This is an exciting prospect but to realise the goal of low carbon-intensity fuel economy breakthroughs are required for both fuel generation and utilisation systems. Current materials for CO2 reduction and water oxidation do not achieve the required level of efficiency and stability at a viable cost. Similarly the most promising clean technologies for electricity generation on demand from carbon fuels, fuel cells, often suffer from relatively low efficiencies and intolerances to impurities in the fuel feed.The original fellowship has been highly successful in delivering new low-cost catalysts that can either be driven directly by sunlight (photocatalysts) or indirectly using electrical energy (which could in principle come from a PV panel) to reduce CO2 to CO, an important liquid fuel precursor. Part of the original fellowship developed new capabilities within the UK for a highly sensitive surface sensitive spectroscopy, IR-Vis Sum Frequency Generation Spectroscopy. This experiment has been used to identify with an incredible level of detail the mechanisms of catalysts at surfaces. These, and our wider spectroscopic studies, have been critical in guiding our own catalyst design programme. But the need for mechanistic insights extends beyond our own synthetic programme. A lack of understanding of the mechanisms of catalysis occurring on the surface of electrodes and photoelectrodes is a limiting factor for the entire field preventing the rational development of new materials. Therefore our spectroscopy driven programme will be expanded to address both the crucial reactions of fuel generation (water oxidation and CO2 reduction) as well as to fuel utilisation chemistry, through the study of state of the art metal-oxide fuel cells. The project is ambitious, aiming not just to provide the first identification of all key intermediates during water oxidation on the most commonly studied photoelectrode (hematite), but also to explore how secondary interactions with water and electrolyte salts control the activity. A similar level of mechanistic detail is also sought from leading CO2 reduction catalysts and fuel cell electrodes. This level of mechanistic detail that we aim to deliver could be transformative to our own, collaborators and the wider communities programmes of material development. The delivery of scalable, efficient materials for solar fuels production and utilisation is a challenging goal but the potential impact is enormous. An improved understanding of surface mechanisms on current materials would represent an important step towards this ambition.