Strong Metal–Support Interaction for 2D Materials: Application in Noble Metal/TiB₂ Heterointerfaces and their Enhanced Catalytic Performance for Formic Acid Dehydrogenation

Abstract

Strong metal–support interaction (SMSI) is a phenomenon commonly observed on heterogeneous catalysts. Here, direct evidence of SMSI between noble metal and 2D TiB2 supports is reported. The temperature‐induced TiB2 overlayers encapsulate the metal nanoparticles, resulting in core–shell nanostructures that are sintering‐resistant with metal loadings as high as 12.0 wt%. The TiOx‐terminated TiB2 surfaces are the active sites catalyzing the dehydrogenation of formic acid at room temperature. In contrast to the trade‐off between stability and activity in conventional SMSI, TiB2‐based SMSI promotes catalytic activity and stability simultaneously. By optimizing the thickness and coverage of the overlayer, the Pt/TiB2 catalyst displays an outstanding hydrogen productivity of 13.8 mmol g−1cat h−1 in 10.0 m aqueous solution without any additive or pH adjustment, with >99.9% selectivity toward CO2 and H2. Theoretical studies suggest that the TiB2 overlayers are stabilized on different transition metals through an interplay between covalent and electrostatic interactions. Furthermore, the computationally determined trends in metal–TiB2 interactions are fully consistent with the experimental observations regarding the extent of SMSI on different transition metals. The present research introduces a new means to create thermally stable and catalytically active metal/support interfaces for scalable chemical and energy applications.

Surface-oxidized titanium diboride as cocatalyst on hematite photoanode for solar water splitting

“…The binding energy at 188.1 eV belongs to the B in TiB 2 , and the binding energy at 192.1 eV is attributed to metaborate (BO x ) species. 30,31 32,33 XPS analysis confirms that we successfully loaded TiB 2 on the surface of α-Fe 2 O 3 ; the surface oxidized layer is composed of BO x by subsequent calcination process, in accordance with the result of HRTEM.…”

“…There are two peaks for α-Fe 2 O 3 , containing lattice oxygen (529.8 eV) and hydroxyl groups (531.3 eV). But the O 1s spectra of α-Fe 2 O 3 /SO-TiB 2 could be divided into lattice oxygen (530.1 eV), B-O bond (532.3 eV) and hydroxyl groups (531.5 eV) 32,33. XPS analysis confirms that we successfully loaded TiB 2 on the surface of α-Fe 2 O 3 ; the surface oxidized layer is composed of BO x by subsequent calcination process, in accordance with the result of HRTEM.…”

Manipulating Intermediates at the Au–TiO2 Interface over InP Nanopillar Array for Photoelectrochemical CO2 Reduction

“…We found that interfacial properties like the adhesion energies on two-, three-, and four-layered TiO 2 supports are almost identical (see the Supporting Information). A dipole correction along the z -direction is used to avoid spurious electrostatic interactions between periodic slabs separated by a vacuum. , We employed numerical cutoffs for total energies and forces of 10 –7 eV and 0.05 eV Å –1 , respectively. We applied a Fermi Dirac smearing of 0.1 eV to the electronic states to facilitate numerical convergence of the self-consistent loop.…”

Formic Acid to Power towards Low‐Carbon Economy

“…Li et al have optimized MSI on Pt loaded on layered TiB 2 (Pt/TiB2, 16) to yield hydrogen productivity of 13.8 mmol g cat −1 h −1 in 10 M FA solution under additive-free conditions. [80] On the other hand, Pd catalysts supported nanoporous carbon (Pd/C; 17) have shown the TOF of 9110 h −1 at 60 °C using an equimolar FA-SF (sodium formate) solution. [81] Monometallic nanoparticles with strong CO adsorption strengths are prone to deactivation in the aqueous phase FA dehydrogenation due to poisoning.…”