Factors governing the protonation of Keggin-type polyoxometalates: influence of the core structure in clusters.

Atomic substitution is a promising approach for controlling structures and properties for developing clusters with desired responses. Although many possible coordination candidates could be deduced for substitution, not all can be prepared. Therefore, predicting the correlation between structures and physical properties is important prior to synthesis. In this study, regarding Keggin-type polyoxometalates (POMs) as a model cluster, the dominant factors affecting the protonation were investigated by atomic substitutions and geometry changes. The valence of Keggin-type POMs and the constituent elements of the cluster shell structure affect the charge and potential distribution, which change the protonation sites. Furthermore, the valence of Keggin-type POMs and the bond length between the core and shell structure determine the protonation energy. These factors also affect the HOMO-LUMO gap, which governs photochemical and redox reactions. These governing factors derived from actual parameters of the α-isomer of Keggin-type POMs enabled us to deduce the protonation energy of the ß-isomer, which is more difficult to prepare and isolate than the α-isomer.

Effect of CeO2 support structure on the catalytic performance of ammonia synthesis in an electric field at low temperatures.

Ammonia is an extremely important storage and transport medium for renewable energy, and technology is expected to produce it on demand and onsite using renewable energy. Applying a DC (direct current) to a solid catalyst layer with semiconducting properties makes ammonia synthesis highly efficient, even at low temperatures (approximately 400 K). In this process, oxide supports with semiconducting properties play important roles as metal supports and conduction fields for electrons and protons. The influence of the degree of particle aggregation on the support properties and ammonia synthesis using an electric field was evaluated for CeO2, which is the best material for this purpose because of its semiconducting properties. The results showed that controlling the aggregation structure of the crystalline particles could significantly influence the surface conductivity of protons and electrons; thus, the activity could be largely controlled. The Ru-CeO2 interaction could also be controlled by changing the crystallinity, which suppressed the aggregation of the supported Ru and significantly improved the ammonia synthesis activity using an electric field at low temperatures.

Equilibrium unconstrained low-temperature CO2 conversion on doped gallium oxides by chemical looping.

Reverse water gas shift (RWGS) can convert CO2 into CO by using renewable hydrogen. However, this important reaction is endothermic and equilibrium constrained, and thus traditionally performed at 900 K or higher temperatures using solid catalysts. In this work, we found that RWGS can be carried out at low temperatures without equilibrium constraints using a redox method called chemical looping (CL), which uses the reduction and oxidation of solid oxide surfaces. When using our developed MGa2Ox (M = Ni, Cu, Co) materials, the reaction can proceed with almost 100% CO2 conversion even at temperatures as low as 673 K. This allows RWGS to proceed without equilibrium constraints at low temperatures and greatly decreases the cost for the separation of unreacted CO2 and produced CO. Our novel gallium-based material is the first material that can achieve high conversion rates at low temperatures in reverse water gas shift using chemical looping (RWGS-CL). Ni outperformed Cu and Co as a dopant, and the redox mechanism of NiGa2Ox is a phase change due to the redox of Ga during the RWGS-CL process. This major finding is a big step forward for the effective utilization of CO2 in the future.

Quantum Annealing Boosts Prediction of Multimolecular Adsorption on Solid Surfaces Avoiding Combinatorial Explosion.

Quantum annealing has been used to predict molecular adsorption on solid surfaces. Evaluation of adsorption, which takes place in all solid surface reactions, is a crucially important subject for study in various fields. However, predicting the most stable coordination by theoretical calculations is challenging for multimolecular adsorption because there are numerous candidates. This report presents a novel method for quick adsorption coordination searches using the quantum annealing principle without combinatorial explosion. This method exhibited much faster search and more stable molecular arrangement findings than conventional methods did, particularly in a high coverage region. We were able to complete a configurational prediction of the adsorption of 16 molecules in 2286 s (including 2154 s for preparation, only required once), whereas previously it has taken 38 601 s. This approach accelerates the tuning of adsorption behavior, especially in composite materials and large-scale modeling, which possess more combinations of molecular configurations.

Theoretical investigation of selective CO2 capture and desorption controlled by an electric field.

Low-cost carbon dioxide (CO2) capture technologies have been studied widely. Among such technologies, the control of CO2 adsorption by the application of an electric field to solid materials has been shown to be a promising technology that can combine high CO2 adsorption with low energy consumption. Suitable materials must be found for electric field-assisted CO2 adsorption. For this study, the CO2 adsorption energies of CeO2 partially substituted with hetero-cations were investigated using theoretical calculations. The differences in adsorption performance attributable to the application of an electric field were clarified for different doped cations. The results show that the amount of change in the CO2 adsorption energy by the application of an electric field depended on the different doped cations. Furthermore, it is found that this difference in cations is related to the electronegativity of the doped cations. These results suggest a tuning strategy for the material properties necessary for CO2 capture and separation using an electric field.

Evaluating the effects of OH-groups on the Ni surface on low-temperature steam reforming in an electric field.

The effect of OH-groups on the surface of a Ni catalyst for low-temperature (473 K) steam reforming of methane in an electric field (EF) was investigated. Ni-doped YSZ (Zr0.65Y0.05Ni0.3O2) was chosen as a highly active catalyst for this purpose. The effects on catalyst activity of adding hydrogen and steam in the pre-treatment were assessed with and without EF. When an EF was applied, activity increased irrespective of the electronic state of Ni, whereas the metallic Ni state was necessary for activity without EF. Furthermore, the highest activity with EF was observed for the pre-treatment with a mixture of H2 and H2O. Investigation of the superiority using XPS measurements showed an increase in the amount of Ni(OH)2, OH groups and H2O near the surface after the activity test, which are regarded as the reaction sites with EF. This finding suggests that a pre-treatment with steam increases the surface OH groups and Ni(OH)2 on the Ni catalyst, and enhances surface proton conduction, thereby improving the activity.

Elucidation of the reaction mechanism on dry reforming of methane in an electric field by in situ DRIFTs.

With increasing expectations for carbon neutrality, dry reforming is anticipated for direct conversion of methane and carbon dioxide: the main components of biogas. We have found that dry reforming of methane in an electric field using a Pt/CeO2 catalyst proceeds with sufficient rapidity even at a low temperature of about 473 K. The effect of the electric field (EF) on dry reforming was investigated using kinetic analysis, in situ DRIFTs, XPS, and DFT calculation. In situ DRIFTs and XPS measurements indicated that the amount of carbonate, which is an adsorbed species of CO2, increased with the application of EF. XPS measurements also confirmed the reduction of CeO2 by the reaction of surface oxygen and CH4. The reaction between CH4 molecules and surface oxygen was promoted at the interface between Pt and CeO2.

Manipulation of CO adsorption over Me1/CeO2 by heterocation doping: Key roles of single-atom adsorption energy.

The performance of metal atoms chemically bonded to oxide supports cannot be explained solely by the intrinsic properties of the metals such as the d-band center. Herein, we present an in-depth study of the correlation between metal-oxide interactions and the properties of the supported metal using CO adsorption on Me1 (Fe1, Co1, and Ni1) loaded over CeO2 (111) doped with divalent (Ca, Sr, and Ba), trivalent (Al, Ga, Sc, Y, and La), and quadrivalent (Hf and Zr) heterocations. CO adsorption over Me1 is strongly dependent on the binding energies of Me1. Two factors led to this trend. First, the extent of the Me1-surface oxygen (Me1-O) bond relaxation during CO adsorption played a key role. Second, the d-band center shifted drastically because of charge transfer to the oxides. The shift is related to the oxophilicity of metals. Adsorption energies of Me1 over oxides include the contributions of the factors described above. Therefore, we can predict the activities of Me1 using the strength of anchoring by oxide supports. Results show that smaller ionic radii of the doped heterocations were associated with more tightly bound Me1. This finding sheds light on the possibility of heterocation-doping manipulating the reactivity of the Me1 catalyst based on theoretical predictions.

Theoretical prediction by DFT and experimental observation of heterocation-doping effects on hydrogen adsorption and migration over the CeO2(111) surface.

Hydrogen (H) atom adsorption and migration over the CeO2-based materials surface are of great importance because of its wide applications to catalytic reactions and electrochemical devices. Therefore, comprehensive knowledge for controlling the H atom adsorption and migration over CeO2-based materials is crucially important. For controlling H atom adsorption and migration, we investigated irreducible divalent, trivalent, and quadrivalent heterocation-doping effects on H atom adsorption and migration over the CeO2(111) surface using density functional theory (DFT) calculations. Results revealed that the electron-deficient lattice oxygen (Olat) and the flexible CeO2 matrix played key roles in strong adsorption of H atoms. Heterocations with smaller valence and smaller ionic radius induced the electron-deficient Olat. In addition, smaller cation doping enhanced the CeO2 matrix flexibility. Moreover, we confirmed the influence of H atom adsorption controlled by doping on surface proton migration (i.e. surface protonics) and catalytic reaction involving surface protonics (NH3 synthesis in an electric field). Results confirmed clear correlation between H atom adsorption energy and surface protonics.