Assessing Exchange-Correlation Functionals for Heterogeneous Catalysis of Nitrogen Species.

Increasing interest in the sustainable synthesis of ammonia, nitrates, and urea has led to an increase in studies of catalytic conversion between nitrogen-containing compounds using heterogeneous catalysts. Density functional theory (DFT) is commonly employed to obtain molecular-scale insight into these reactions, but there have been relatively few assessments of the exchange-correlation functionals that are best suited for heterogeneous catalysis of nitrogen compounds. Here, we assess a range of functionals ranging from the generalized gradient approximation (GGA) to the random phase approximation (RPA) for the formation energies of gas-phase nitrogen species, the lattice constants of representative solids from several common classes of catalysts (metals, oxides, and metal-organic frameworks (MOFs)), and the adsorption energies of a range of nitrogen-containing intermediates on these materials.

Gradient area-selective deposition for seamless gap-filling in 3D nanostructures through surface chemical reactivity control.

The integration of bottom-up fabrication techniques and top-down methods can overcome current limits in nanofabrication. For such integration, we propose a gradient area-selective deposition using atomic layer deposition to overcome the inherent limitation of 3D nanofabrication and demonstrate the applicability of the proposed method toward large-scale production of materials. Cp(CH)Ti(OMe) is used as a molecular surface inhibitor to prevent the growth of TiO film in the next atomic layer deposition process.