CuNi Nanoalloys with Tunable Composition and Oxygen Defects for the Enhancement of the Oxygen Evolution Reaction.

Colloidal synthesis is an excellent tool for the study of cooperative effects in nanoalloys. In this work, bimetallic CuNi nanoparticles of defined size and composition are fully characterized and tested for the oxygen evolution reaction. Copper addition to nickel leads to modifications in the structural and electronic properties, showing a higher concentration of surface oxygen defects and formation of active Ni3+ sites under reaction conditions. The ratio OV /OL between oxygen vacancies and lattice oxygen shows a clear correlation with the overpotential, being an excellent descriptor of the electrocatalytic activity. This is attributed to modifications in the crystalline structure, leading to lattice strain and grain size effects. Bimetallic Cu50 Ni50 NP showed the lowest overpotential (318 mV vs RHE), low Tafel slope (63.9 mV dec-1 ), and excellent stability. This work unravels the relative concentration between oxygen defects and lattice oxygen (OV /OL ) as an excellent descriptor of the catalytic activity of bimetallic precatalysts.

Mechanistic studies of atomic layer deposition on oxidation catalysts - AlOx and POx deposition.

Atomic layer deposition is a rising technique for catalyst synthesis and modification. Typically, the focus of ALD in catalysis is on supported metal nanoparticles. Here, the authors give mechanistic insights into the ALD of oxides on redox active catalysts by a combination of in situ analytics, such as XPS, DRIFTS and gravimetric measurements. Phosphorus oxide and aluminum oxide were deposited on divanadium pentoxide powder in a fixed bed reactor. In contrast to the generally accepted concepts, the first half cycle does not proceed over surface hydroxyl groups but involves redox chemistry between the precursor and the vanadium atoms, as shown by 31P-SSNMR and XPS. For POx deposition, a temperature step from 150 °C in the first half cycle to 450 °C in the second half cycle is needed to obtain linear mass gain per cycle as the remaining ligands are combusted and reduced vanadium atoms are reoxidized. Homogeneous deposition was confirmed by STEM-EDX and XRD showing no additional phases, despite performing up to 10 ALD cycles. Even the well-known process of alumina ALD confirms the involvement of reduction-oxidation reactions between the ALD precursor and the substrate V2O5. However, redox chemistry can be suppressed for alumina ALD at low temperatures of 50 °C. Therefore, this study shows that ALD on oxidation catalysts is complex and thus the developed ALD processes are unusual compared to ALD on typical supports, such as SiO2 or Al2O3.

Synthesis of High Surface Area-Group 13-Metal Oxides via Atomic Layer Deposition on Mesoporous Silica.

The atomic layer deposition of gallium and indium oxide was investigated on mesoporous silica powder and compared to the related aluminum oxide process. The respective oxide (GaOx, InOx) was deposited using sequential dosing of trimethylgallium or trimethylindium and water at 150 °C. In-situ thermogravimetry provided direct insight into the growth rates and deposition behavior. The highly amorphous and well-dispersed nature of the oxides was shown by XRD and STEM EDX-mappings. N2 sorption analysis revealed that both ALD processes resulted in high specific surface areas while maintaining the pore structure. The stoichiometry of GaOx and InOx was suggested by thermogravimetry and confirmed by XPS. FTIR and solid-state NMR were conducted to investigate the ligand deposition behavior and thermogravimetric data helped estimate the layer thicknesses. Finally, this study provides a deeper understanding of ALD on powder substrates and enables the precise synthesis of high surface area metal oxides for catalytic applications.

Atomic Layer Deposition of ZnO on Mesoporous Silica: Insights into Growth Behavior of ZnO via In-Situ Thermogravimetric Analysis.

ZnO is a remarkable material with many applications in electronics and catalysis. Atomic layer deposition (ALD) of ZnO on flat substrates is an industrially applied and well-known process. Various studies describe the growth of ZnO layers on flat substrates. However, the growth characteristics and reaction mechanisms of atomic layer deposition of ZnO on mesoporous powders have not been well studied. This study investigates the ZnO ALD process based on diethylzinc (DEZn) and water with silica powder as substrate. In-situ thermogravimetric analysis gives direct access to the growth rates and reaction mechanisms of this process. Ex-situ analytics, e.g., N2 sorption analysis, XRD, XRF, HRTEM, and STEM-EDX mapping, confirm deposition of homogenous and thin films of ZnO on SiO2. In summary, this study offers new insights into the fundamentals of an ALD process on high surface area powders.

Investigating the Trimethylaluminium/Water ALD Process on Mesoporous Silica by In Situ Gravimetric Monitoring.

A low amount of AlOx was successfully deposited on an unordered, mesoporous SiO2 powder using 1⁻3 ALD (Atomic Layer Deposition) cycles of trimethylaluminium and water. The process was realized in a self-built ALD setup featuring a microbalanceand a fixed particle bed. The reactor temperature was varied between 75, 120, and 200 °C. The self-limiting nature of the deposition was verified by in situ gravimetric monitoring for all temperatures. The coated material was further analyzed by nitrogen sorption, inductively coupled plasma-optical emission spectroscopy, powder X-ray diffraction, high-resolution transmission electron microscopy, attenuated total reflection Fourier transformed infrared spectroscopy, and elemental analysis. The obtained mass gains correspond to average growth between 0.81⁻1.10 Å/cycle depending on substrate temperature. In addition, the different mass gains during the half-cycles in combination with the analyzed aluminum content after one, two, and three cycles indicate a change in the preferred surface reaction of the trimethylaluminium molecule from a predominately two-ligand exchange with hydroxyl groups to more single-ligand exchange with increasing cycle number. Nitrogen sorption isotherms demonstrate (1) homogeneously coated mesopores, (2) a decrease in surface area, and (3) a reduction of the pore size. The experiment is successfully repeated in a scale-up using a ten times higher substrate batch size.

Coverage-dependent kinetics and thermodynamics of carbon monoxide adsorption on a ternary copper catalyst derived from static adsorption microcalorimetry.

A reliable method for adsorption systems in equilibrium is established to derive coverage-dependent kinetics and thermodynamics from the volumetric data obtained during the static microcalorimetric measurement of heats of adsorption. The Wigner-Polanyi equation is applied to analyze the pressure change as a function of time during stepwise dosing of the adsorptive until thermodynamic adsorption-desorption equilibrium is established. For carbon monoxide adsorption on a hydrogen-reduced Cu/ZnO/Al2O3 catalyst, the adsorption rate constant (ka) is found to be in the range from 10(-6) to 10(-4) Pa(-1) s(-1), and the desorption rate constant (kd) from 10(-4) to 10(-2) s(-1), both increasing with fractional coverage theta. The kinetically derived equilibrium constant Ktheta is in good agreement with Ktheta obtained from the adsorption isotherm. RT ln(Kp0) and the differential heat of adsorption (qdiff) were found to decrease in parallel, reflecting a normal Temkin-type heterogeneity.