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.

由于资源限制和石油经济对气候的影响，能源生产成本的情况变得更具挑战性，能够将阳光转化为工业上可行的形式（例如电力）的新材料和技术的潜在相关性电力或化学燃料至关重要。这种能量转换的关键是光催化剂 (PC) 的存在。PC 是符合以下条件的化合物：首先，它们吸收光，光的能量（与其光子的频率相关）用于激发一个电子（e ）将 PC 提升到更高能态 (e*)，在原始电子态中留下一个空穴 (h)。一旦光子被吸收，并产生一对 e*-h，可能会发生几个竞争过程：1) e*-h 对可能引起化合物的分解； 2) e*-h 对可以在 e* 衰变之前通过发射一个光子将其部分能量释放到核振动中，从而与 h 重新结合，或 3) e* 和 h 可以分别与其他原子反应分子或进入电路。因此，可行的 PC 的特点是光稳定性，并且 e*-h 重组速率比 e*-h 对单独与其他物种反应所需的时间慢。通常，e* 距离 h 越远，e*-h 重组就越慢。 PC的化学优雅之处在于，由于吸收了光子能量，e*-h对具有高反应性，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，那么个人电脑可以将太阳能作为地球上的燃料，从而促进能源生产。值得注意的是，存储在 e*-h 对中的能量原则上也可用于其他能源昂贵的应用，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。该研究的重点是开放式金属氧化物纳米管 (MONT)，这是一种由 Al (Ge)、Si、O 和 H 制成的高分子管。该项目建立在有关创建 e*-h 可能性的最新发现的基础上一对在不同的侧面MONT 墙应根据 PC 的要求提供相当长的 e*-h 重组时间。这些系统的初步模拟表明，还应该可以将其他原子（掺杂剂）插入 MONT 壁中。预计掺杂剂的化学性质将影响掺杂 MONT (dMONT) 的光催化性能。拟议的研究旨在确定 dMONT 结构与其光活性之间关系的关键方面。然后，这一见解将用于优化 dMONT 的侧依赖性光催化性能，特别关注 e*-h 化学相对于 e*-h 重组的增强。理论研究将依赖于求解 dMONT 电子和原子核的量子力学运动方程，以表征其几何和电子特性。这将允许识别具有最大 e*-h 分离和对 e*-h 转移到其他物种的最大亲和力的系统。还将获得有关为特定 dMONTS 生成 e*-h 对所需的光能的理论和实验见解。最后，对 dMONT 中 e*-h 时间演化的模拟将深入了解控制 e*-h 重组和 e*-h 转移之间竞争的因素，这将使得有可能选择性地挫败前者，同时增强后者，从而提高了 dMONT 的光催化性能。这些知识将为基于 dMONT 的应用开辟道路，这些应用对我们的经济很重要，例如燃料生产、工业目标 PC 和污染废物分解。

项目成果

Role of Metal Lattice Expansion and Molecular p-Conjugation for the Magnetic Hardening at Cu-Organics Interfaces.

金属晶格膨胀和分子 p 共轭对铜有机物界面磁硬化的作用。

• DOI: http://dx.10.1021/acs.jpcc.7b08476
• 发表时间: 2017
• 期刊: The journal of physical chemistry. C, Nanomaterials and interfaces
• 作者: Martín

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

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

用于偏振增强光催化的光铁电体的化学选择性替代品：混合无机纳米管的未开发潜力。

• DOI: http://dx.10.1002/advs.201600153
• 发表时间: 2017
• 期刊: Advanced science (Weinheim, Baden-Wurttemberg, Germany)
• 作者: Elliott JD

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

密度泛函理论筛选稳定高能量密度锂金属阳极的气体处理策略

• DOI: 10.1016/j.jpowsour.2015.07.027
• 发表时间: 2015-05-29
• 期刊: Journal of Power Sources
• 影响因子: 9.2
• 作者: S. Koch;B. Morgan;S. Passerini;G. Teobaldi
• 通讯作者: G. Teobaldi

The effect of temperature on the internal dynamics of dansylated POPAM dendrimers

温度对丹磺酰化 POPAM 树枝状聚合物内部动力学的影响

• DOI: 10.1039/c1ra00625h
• 发表时间: 2011-11-28
• 期刊: RSC Advances
• 影响因子: 3.9
• 作者: Jukka Aumanen;G. Teobaldi;F. Zerbetto;J. Korppi
• 通讯作者: J. Korppi