High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis
High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis
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DOI：
10.1021/acsami.9b01242
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发表时间：
2019-07-17
影响因子：
9.5
通讯作者：
Musgrave, Charles B.
中科院分区：
文献类型：
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作者：
Bartel, Christopher J.;Rumptz, John R.;Musgrave, Charles B.
太阳能热化学氨（NH3）合成（STAS）是从空气、水和集中的太阳光中产生NH3的潜在途径。该过程涉及活性氧化还原对的化学循环，其在金属氮化物和其互补金属氧化物之间循环以产生NH3。为了确定STAS循环的有希望的候选者，我们对1，148个金属氮化物/金属氧化物对进行了高通量热力学筛选。这种数据驱动的筛选是基于晶体金属氧化物和氮化物在高温下的吉布斯能G（T），使用最近引入的统计学学习描述符和材料项目数据库中列出的0 K DFT形成能计算。使用这些预测的G（T）值，我们评估了金属氮化物的水解、金属氧化物的还原和固氮以改革金属氮化物的每个STAS反应的可行性，并分析了在金属氧化物和氮化物之间直接转化的修正循环，这改变了STAS循环的热力学。对于所有1148氧化还原对分析和每个STAS相关的反应，我们实施了吉布斯能量最小化计划，以预测平衡组成和产量的STAS循环，这揭示了新的活性材料的基础上B，V，Fe和Ce，保证进一步调查他们的潜力，介导的STAS循环。这项工作详细介绍了一种高通量的方法来评估热化学氧化还原过程的相关温度依赖性热力学，该方法利用了使用DFT计算的公开可用的与温度无关的热力学数据。这种方法很容易适应于发现针对热化学应用的最佳材料，并能够使用热控制的固态反应预测合成新化合物。
Solar thermochemical ammonia (NH3) synthesis (STAS) is a potential route to produce NH3 from air, water, and concentrated sunlight. This process involves the chemical looping of an active redox pair that cycles between a metal nitride and its complementary metal oxide to yield NH3. To identify promising candidates for STAS cycles, we performed a high-throughput thermodynamic screening of 1,148 metal nitride/metal oxide pairs. This data-driven screening was based on Gibbs energies of crystalline metal oxides and nitrides at elevated temperatures, G(T), calculated using a recently introduced statistically learned descriptor and 0 K DFT formation energies tabulated in the Materials Project database. Using these predicted G(T) values, we assessed the viability of each of the STAS reactions hydrolysis of the metal nitride, reduction of the metal oxide, and nitrogen fixation to reform the metal nitride and analyzed a revised cycle that directly converts between metal oxides and nitrides, which alters the thermodynamics of the STAS cycle. For all 1148 redox pairs analyzed and each of the STAS-relevant reactions, we implemented a Gibbs energy minimization scheme to predict the equilibrium composition and yields of the STAS cycle, which reveals new active materials based on B, V, Fe, and Ce that warrant further investigation for their potential to mediate the STAS cycle. This work details a high-throughput approach to assessing the relevant temperature-dependent thermodynamics of thermochemical redox processes that leverages the wealth of publicly available temperature-independent thermodynamic data calculated using DFT. This approach is readily adaptable to discovering optimal materials for targeted thermochemical applications and enabling the predictive synthesis of new compounds using thermally controlled solid-state reactions.