Related Articles
Modeling the impact of structure and coverage on the reactivity of realistic heterogeneous catalysts
Adsorbates often cover the surfaces of catalysts densely as they carry out reactions, dynamically altering their structure and reactivity. Understanding adsorbate-induced phenomena and harnessing them in our broader quest for improved catalysts is a substantial challenge that is only beginning to be addressed. Here we chart a path toward a deeper understanding of such phenomena by focusing on emerging in silico modeling methodologies, which will increasingly incorporate machine learning techniques. We first examine how adsorption on catalyst surfaces can lead to local and even global structural changes spanning entire nanoparticles, and how this affects their reactivity. We then evaluate current efforts and the remaining challenges in developing robust and predictive simulations for modeling such behavior. Last, we provide our perspectives in four critical areas—integration of artificial intelligence, building robust catalysis informatics infrastructure, synergism with experimental characterization, and adaptive modeling frameworks—that we believe can help surmount the remaining challenges in rationally designing catalysts in light of these complex phenomena.
A catalyst-coated diaphragm assembly to improve the performance and energy efficiency of alkaline water electrolysers
Alkaline water electrolysers are ideal for gigawatt-scale hydrogen production due to the usage of non-precious metal and low-cost raw materials. However, their performances are modest with the separated electrode and diaphragm structure which can date back to more than 100 years ago. Here we report a catalyst-coated diaphragm assembly to improve the performance of alkaline water electrolysers. The transport resistance of OH– ions is reduced and the electrochemical surface area of catalysts is enlarged by more than forty fold, representing more than 40% increase in hydrogen production rate or as much as 16% reduction in energy consumption. The electrolyser with our catalyst-coated diaphragm assembly delivers current densities as high as 1 A cm−2 at 1.8 V or 2 A cm−2 at 2 V and shows good stability after more than 1000 hours of operation. Therefore, the catalyst-coated diaphragm assembly route is promising for the development of high-performance and efficient alkaline water electrolysers.
Perovskite-driven solar C2 hydrocarbon synthesis from CO2
Photoelectrochemistry (PEC) presents a direct pathway to solar fuel synthesis by integrating light absorption and catalysis into compact electrodes. Yet, PEC hydrocarbon production remains elusive due to high catalytic overpotentials and insufficient semiconductor photovoltage. Here we demonstrate ethane and ethylene synthesis by interfacing lead halide perovskite photoabsorbers with suitable copper nanoflower electrocatalysts. The resulting perovskite photocathodes attain a 9.8% Faradaic yield towards C2 hydrocarbon production at 0 V against the reversible hydrogen electrode. The catalyst and perovskite geometric surface areas strongly influence C2 photocathode selectivity, which indicates a role of local current density in product distribution. The thermodynamic limitations of water oxidation are overcome by coupling the photocathodes to Si nanowire photoanodes for glycerol oxidation. These unassisted perovskite–silicon PEC devices attain partial C2 hydrocarbon photocurrent densities of 155 µA cm−2, 200-fold higher than conventional perovskite–BiVO4 artificial leaves for water and CO2 splitting. These insights establish perovskite semiconductors as a versatile platform towards PEC multicarbon synthesis.
Anion vacancies activate N2 to ammonia on Ba–Si orthosilicate oxynitride-hydride
Anion vacancies on metal oxide surfaces have been studied as either active sites or promoting sites in various chemical reactions involving oxidation/reduction processes. However, oxide materials rarely work effectively as catalysts in the absence of transition metal sites. Here we report a Ba–Si orthosilicate oxynitride–hydride as a transition-metal-free catalyst for efficient ammonia synthesis via an anion-vacancy–mediated mechanism. The facile desorption of H− and N3− anions plus the flexibility of the crystal structure can accommodate a high density of electrons at vacancy sites, where N2 can be captured and directly activated to ammonia through hydrogenation processes. The ammonia synthesis rates reach 40.1 mmol g−1 h−1 at 300 °C by loading ruthenium nanoparticles. Although not found to dissociate N2, Ru instead facilitates the formation of anion vacancies at the Ru–support interface. This demonstrates a new route for anion-vacancy–mediated heterogeneous catalysis.
Global self-organization of solute induced by ion irradiation in polycrystalline alloys
Most materials are brought into nonequilibrium states during processing and during their service life. Materials for nuclear and space applications, for instance, are continuously exposed to energetic particle irradiation, which is often detrimental to materials’ performance. Here we demonstrate, however, that sustained irradiation can induce self-organization of the microstructure of polycrystalline alloys into steady-state patterns and, in turn, improve their radiation resistance. Using an Al −1.5 at.% Sb alloy as a model system, we show using transmission electron microscopy and atom probe tomography that, for nanocrystalline thin films irradiated at 75 °C with 2 MeV Ti ions to large doses, the microstructure consists of finite-size, self-organized AlSb nanoprecipitates inside the grains and along the grain boundaries. Furthermore, this steady state is independent of the initial microstructure, thus self-healing. Phase field modeling is employed to construct a steady-state phase diagram and extend the experimental results to other alloy systems and microstructures.
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