Synthesis, Computed Stability, and Crystal Structure of a New Family of Inorganic Compounds: Carbonophosphates

<i>Ab initio</i>-based high-throughput computing and screening are now being used to search and predict new functional materials and novel compounds. However, systematic experimental validation on the predictions remains highly challenging, yet desired. Careful comparison between computational predictions and experimental results is sparse in the literature. Here we report on a systematic experimental validation on previously presented computational predictions of a novel alkali carbonophosphate family of compounds. We report the successful hydrothermal synthesis and structural characterization of multiple sodium carbonophosphates. The experimental conditions for formation of the carbonophosphates and the computational results are compared and discussed. We also demonstrate topotactic chemical de-sodiation of one of the compounds, indicating the potential use of this novel class of compounds as Li⁺ or Na⁺ insertion electrodes

Dioscorea sativa

<i>Ab initio</i>-based high-throughput computing and screening are now being used to search and predict new functional materials and novel compounds. However, systematic experimental validation on the predictions remains highly challenging, yet desired. Careful comparison between computational predictions and experimental results is sparse in the literature. Here we report on a systematic experimental validation on previously presented computational predictions of a novel alkali carbonophosphate family of compounds. We report the successful hydrothermal synthesis and structural characterization of multiple sodium carbonophosphates. The experimental conditions for formation of the carbonophosphates and the computational results are compared and discussed. We also demonstrate topotactic chemical de-sodiation of one of the compounds, indicating the potential use of this novel class of compounds as Li⁺ or Na⁺ insertion electrodes

Synthesis, Computed Stability, and Crystal Structure of a New Family of Inorganic Compounds: Carbonophosphates

<i>Ab initio</i>-based high-throughput computing and screening are now being used to search and predict new functional materials and novel compounds. However, systematic experimental validation on the predictions remains highly challenging, yet desired. Careful comparison between computational predictions and experimental results is sparse in the literature. Here we report on a systematic experimental validation on previously presented computational predictions of a novel alkali carbonophosphate family of compounds. We report the successful hydrothermal synthesis and structural characterization of multiple sodium carbonophosphates. The experimental conditions for formation of the carbonophosphates and the computational results are compared and discussed. We also demonstrate topotactic chemical de-sodiation of one of the compounds, indicating the potential use of this novel class of compounds as Li⁺ or Na⁺ insertion electrodes

Synthesis, Computed Stability, and Crystal Structure of a New Family of Inorganic Compounds: Carbonophosphates

<i>Ab initio</i>-based high-throughput computing and screening are now being used to search and predict new functional materials and novel compounds. However, systematic experimental validation on the predictions remains highly challenging, yet desired. Careful comparison between computational predictions and experimental results is sparse in the literature. Here we report on a systematic experimental validation on previously presented computational predictions of a novel alkali carbonophosphate family of compounds. We report the successful hydrothermal synthesis and structural characterization of multiple sodium carbonophosphates. The experimental conditions for formation of the carbonophosphates and the computational results are compared and discussed. We also demonstrate topotactic chemical de-sodiation of one of the compounds, indicating the potential use of this novel class of compounds as Li⁺ or Na⁺ insertion electrodes

Synthesis, Computed Stability, and Crystal Structure of a New Family of Inorganic Compounds: Carbonophosphates

<i>Ab initio</i>-based high-throughput computing and screening are now being used to search and predict new functional materials and novel compounds. However, systematic experimental validation on the predictions remains highly challenging, yet desired. Careful comparison between computational predictions and experimental results is sparse in the literature. Here we report on a systematic experimental validation on previously presented computational predictions of a novel alkali carbonophosphate family of compounds. We report the successful hydrothermal synthesis and structural characterization of multiple sodium carbonophosphates. The experimental conditions for formation of the carbonophosphates and the computational results are compared and discussed. We also demonstrate topotactic chemical de-sodiation of one of the compounds, indicating the potential use of this novel class of compounds as Li⁺ or Na⁺ insertion electrodes

Synthesis, Computed Stability, and Crystal Structure of a New Family of Inorganic Compounds: Carbonophosphates

<i>Ab initio</i>-based high-throughput computing and screening are now being used to search and predict new functional materials and novel compounds. However, systematic experimental validation on the predictions remains highly challenging, yet desired. Careful comparison between computational predictions and experimental results is sparse in the literature. Here we report on a systematic experimental validation on previously presented computational predictions of a novel alkali carbonophosphate family of compounds. We report the successful hydrothermal synthesis and structural characterization of multiple sodium carbonophosphates. The experimental conditions for formation of the carbonophosphates and the computational results are compared and discussed. We also demonstrate topotactic chemical de-sodiation of one of the compounds, indicating the potential use of this novel class of compounds as Li⁺ or Na⁺ insertion electrodes

High-Throughput Design of Non-oxide p‑Type Transparent Conducting Materials: Data Mining, Search Strategy, and Identification of Boron Phosphide

High-performance p-type transparent conducting materials (TCMs) are needed in a wide range of applications ranging from solar cells to transparent electronics. p-type TCMs require a large band gap (for transparency), low hole effective mass (for high mobility), and hole dopability. It has been demonstrated that oxides have inherent limitations in terms of hole effective masses making them difficult to use as a high-performance p-type TCM. In this work, we use a high-throughput computational approach to identify novel, non-oxide, p-type TCMs. By data mining a large computational data set (more than 30,000 compounds), we demonstrate that non-oxide materials can lead to much lower hole effective masses but to the detriment of smaller gaps and lower transparencies. We propose a strategy to overcome this fundamental correlation between low effective mass and small band gap by exploiting the weak absorption for indirect optical transitions. We apply this strategy to phosphides and identify zinc blende boron phosphide (BP) as a very promising candidate. Follow-up computational studies on defects formation indicate that BP can also be doped p-type and potentially n-type as well. Our work demonstrates how high-throughput computational design can lead to identification of materials with exceptional properties, and we propose a strategy to open the design of TCMs to non-oxide materials

Influence of Surface Adsorption on the Oxygen Evolution Reaction on IrO₂(110)

A catalyst functions by stabilizing reaction intermediates, usually through surface adsorption. In the oxygen evolution reaction (OER), surface oxygen adsorption plays an indispensable role in the electrocatalysis. The relationship between the adsorption energetics and OER kinetics, however, has not yet been experimentally measured. Herein we report an experimental relationship between the adsorption of surface oxygen and the kinetics of the OER on IrO₂(110) epitaxially grown on a TiO₂(110) single crystal. The high quality of the IrO₂ film grown using molecular-beam epitaxy affords the ability to extract the surface oxygen adsorption and its impact on the OER. By examining a series of electrolytes, we find that the adsorption energy changes linearly with pH, which we attribute to the electrified interfacial water. We support this hypothesis by showing that an electrolyte salt modification can lead to an adsorption energy shift. The dependence of the adsorption energy on pH has implications for the OER kinetics, but it is not the only factor; the dependence of the OER electrocatalysis on pH stipulates two OER mechanisms, one operating in acidic solution and another operating in alkaline solution. Our work points to the subtle adsorption–kinetics relationship in the OER and highlights the importance of the interfacial electrified interaction in electrocatalyst design

Carbonophosphates: A New Family of Cathode Materials for Li-Ion Batteries Identified Computationally

The tremendous growth of Li-ion batteries into a wide variety of applications is setting new requirements in terms of cost, energy density, safety, and power density. One route toward meeting these objectives consists in finding alternative chemistries to current cathode materials. In this Article, we describe a new class of materials discovered through a novel high-throughput ab initio computational approach and which can intercalate lithium reversibly. We report on the synthesis, characterization, and electrochemical testing of this novel lithium-carbonophosphate chemistry. This work demonstrates how the novel high-throughput computing approach can identify promising chemistries for next-generation cathode materials

Statistical Analysis of Coordination Environments in Oxides

Coordination or local environments (e.g., tetrahedra and octahedra) are powerful descriptors of the crystalline structure of materials. These structural descriptors are essential to the understanding of crystal chemistry and the design of new materials. However, extensive statistics on the occurrence of local environment are not available even on common chemistries such as oxides. Here, we present the first large-scale statistical analysis of the coordination environments of cations in oxides using a large set of experimentally observed compounds (about 8000). Using a newly developed method, we provide the distribution of local environment for each cation in oxides. We discuss our results highlighting previously known trends and unexpected coordination environments, as well as compounds presenting very rare coordinations. Our work complements the know-how of the solid state chemist with a statistically sound analysis and paves the way for further data mining efforts linking, for instance, coordination environments to materials properties