In-silico development of the potential of doped metal-oxide nanotubes as novel photo-catalysts for energy applications

掺杂金属氧化物纳米管作为能源应用新型光催化剂潜力的计算机开发

• 批准号: EP/I004483/1
• 负责人: Gilberto Teobaldi
• 金额: $ 73.52万
• 依托单位: University of Liverpool
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FI004483%2F1
• 关键词: silico; development; potential; doped; metal

As the situation regarding the costs of energy production becomes more challenging, due to both resource limitation and the impact of an oil-fuelled economy on the climate, the potential relevance of new materials and technologies capable of converting sunlight into industrially viable forms such as electrical power or chemical fuels is paramount. Crucial to this energy conversion is the presence of photo-catalysts (PCs).PCs are compounds which comply with the following: first, they absorb light, whose energy (related to the frequency of its photons) is used to excite one electron (e) of a PC to a higher-energy state (e*) leaving one hole (h) in the pristine electronic state. Once a photon has been absorbed, and one e*-h pair created, several competing processes may take place: 1) the e*-h pair may induce decomposition of the compound; 2) the e*-h pair can release some of its energy into the nuclear vibrations before e* decays, by emission of one photon, to his pristine state thus recombining with h, or 3) e* and h can separately react with other molecules or enter an electric circuit. Thus, viable PCs are characterized by photo-stability, and an e*-h recombination rate slower than the time it takes to the e*-h pair to separately react with other species. Typically, the farther e* is created from h, the slower the e*-h recombination. The chemical elegance of PCs emerge in that, due to the absorbed photon energy, the e*-h pair is highly reactive and may separately reduce-oxidize reactants, thus triggering a redox chemical reaction which can be used to convert light into chemical energy i.e. fuels. If, as it happens for natural photosynthesis, the photon energy comes from the Sun, then PCs can make Sun energy available on Earth as fuels, thus contributing to energy production. Notably, the energy stored in the e*-h pair can in principle be used also for other energetically expensive applications, such as, for instance, the production of ammonia and its derivative, or the decomposition of industrial polluting waste into substances less hazardous for the environment.The research focuses on open-ended metal-oxide nanotubes (MONTs), which are macromolecular tubes made of Al (Ge), Si, O and H. The project builds on recent findings about the possibility to create e*-h pair on different sides of MONTs walls which should provide rather long e*-h recombination times as required for PCs. Preliminary simulations of these systems suggest that it should also be possible to insert other atoms (dopants) into MONTs walls. It is anticipated that the chemical nature of the dopant will influence the photo-catalytic performances of doped MONTs (dMONTs). The proposed research aims at identifying key aspects of the relationship between the structure of dMONTs and their photo-activity. This insight will then be used to optimise dMONTs in terms of side-dependent photo-catalytic performances with special focus on the enhancement of e*-h chemistry over e*-h recombination. The theoretical research will rely on solving the quantum mechanical equations of motion for the electrons and the nuclei of dMONTs in order to characterize their geometrical and electronic properties. This will allow to identify systems with maximum e*-h separation and the largest affinity to e*-h transfer to other species. Theoretical and experimental insight about the light energy required to generate e*-h pairs for specific dMONTS will also be obtained. Finally, simulation of the time evolution of e*-h in dMONTs will provide insight into the factors governing the competition between e*-h recombination, and e*-h transfer which will make it possible to selectively frustrate the former while enhancing the latter, thence boosting the photo-catalytic performance of dMONTs. This knowledge will open the way to possible dMONTs-based applications in many different areas important for our economy such as fuel production, industrially targeted PCs, and decomposition of polluting waste.

由于资源限制和以石油为燃料的经济对气候的影响，能源生产成本的情况变得更具挑战性，因此能够将阳光转化为工业上可行形式（如电力或化学燃料）的新材料和技术的潜在相关性至关重要。这种能量转换的关键是光催化剂（pc）的存在。PC是符合以下原则的化合物：首先，它们吸收光，光的能量（与光子的频率有关）被用来激发PC的一个电子(e)到一个高能态（e*），留下一个空穴(h)处于原始电子状态。一旦光子被吸收，并产生一个e*-h对，就会发生几个相互竞争的过程：1)e*-h对会引起化合物的分解；2) e*-h对可以在e*衰变之前释放一些能量到核振动中，通过发射一个光子，使其回到原始状态，从而与h重新结合，或者3)e*和h可以分别与其他分子反应或进入电路。因此，可行的pc具有光稳定性，并且e*-h重组速率比e*-h对单独与其他物质反应所需的时间要慢。通常，e*离h越远，e*-h的重组就越慢。pc的化学优雅在于，由于吸收光子能量，e*-h对具有高活性，可以单独还原-氧化反应物，从而引发氧化还原化学反应，可用于将光转化为化学能，即燃料。如果像自然光合作用那样，光子能量来自太阳，那么pc就可以使地球上的太阳能成为燃料，从而促进能源生产。值得注意的是，储存在e*-h对中的能量原则上也可以用于其他能量昂贵的应用，例如，氨及其衍生物的生产，或将工业污染废物分解成对环境危害较小的物质。这项研究的重点是开放式金属氧化物纳米管（MONTs），这是一种由Al （Ge）、Si、O和h组成的大分子管。该项目基于最近的发现，即在MONTs壁的不同侧面创建e*-h对的可能性，这将提供pc所需的相当长的e*-h重组时间。这些系统的初步模拟表明，将其他原子（掺杂剂）插入MONTs壁也应该是可能的。预计掺杂剂的化学性质将影响掺杂mont （dMONTs）的光催化性能。提出的研究旨在确定dMONTs结构与其光活性之间关系的关键方面。这一见解将用于优化dMONTs的侧依赖光催化性能，特别关注e*-h化学比e*-h重组的增强。理论研究将依赖于求解dMONTs的电子和原子核的量子力学运动方程，以表征它们的几何和电子性质。这将允许识别系统最大的e*-h分离和最大的亲和力e*-h转移到其他物种。理论和实验的见解，以产生e*-h对特定的dMONTS所需的光能也将获得。最后，对dMONTs中e*-h的时间演化进行模拟，将有助于深入了解控制e*-h重组和e*-h转移之间竞争的因素，从而有可能选择性地抑制e*-h重组，同时增强e*-h转移，从而提高dMONTs的光催化性能。这些知识将为基于dmonts的应用在许多对我们的经济很重要的不同领域开辟道路，比如燃料生产、工业目标pc和污染废物的分解。

项目成果

The role of isotropic and anisotropic Hubbard corrections for the magnetic ordering and absolute band alignment of hematite a-Fe2O3(0001) surfaces

各向同性和各向异性哈伯德校正对赤铁矿 a-Fe2O3(0001) 表面磁有序和绝对能带排列的作用

• DOI: 10.1016/j.pnsc.2019.05.010
• 发表时间: 2019
• 期刊: Materials International
• 作者: Bandaru S

Emergent magnetism at transition-metal-nanocarbon interfaces

• DOI: 10.1073/pnas.1620216114
• 发表时间: 2017-05-30
• 期刊: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• 影响因子: 11.1
• 作者: Al Ma'Mari, Fatma;Rogers, Matthew;Cespedes, Oscar
• 通讯作者: Cespedes, Oscar

Chemically Selective Alternatives to Photoferroelectrics for Polarization-Enhanced Photocatalysis: The Untapped Potential of Hybrid Inorganic Nanotubes.

• DOI: 10.1002/advs.201600153
• 发表时间: 2017-02
• 期刊: Advanced science (Weinheim, Baden-Wurttemberg, Germany)
• 作者: Elliott JD;Poli E;Scivetti I;Ratcliff LE;Andrinopoulos L;Dziedzic J;Hine ND;Mostofi AA;Skylaris CK;Haynes PD;Teobaldi G
• 通讯作者: Teobaldi G

Solid wetting-layers in inorganic nano-reactors: the water in imogolite nanotube case.

• DOI: 10.1039/d0na00128g
• 发表时间: 2020-05-19
• 期刊: Nanoscale advances
• 影响因子: 4.7

Density functional theory screening of gas-treatment strategies for stabilization of high energy-density lithium metal anodes

• DOI: 10.1016/j.jpowsour.2015.07.027
• 发表时间: 2015-05
• 期刊: Journal of Power Sources
• 影响因子: 9.2
• 作者: S. Koch;B. Morgan;S. Passerini;G. Teobaldi