2025

Journal of Physical Chemistry C

Journal year: 2025 | Journal volume: vol. 129 | Journal number: iss. 15

scientific article

english

EN Transition-metal dichalcogenide (TMD) monolayers have emerged as promising materials in electronics, gas sensing, and electrocatalysis. However, the limited chemical reactivity of TMD basal planes constrains their performance due to the lack of coordinatively unsaturated surface sites. Single-atom doping has shown potential to enhance TMD reactivity, though optimal doping strategies remain uncertain due to an incomplete understanding of the mechanisms and selectivity in reactivity enhancement. This study addresses this gap by investigating boron-doped MoTe2 (B-MoTe2)-the most active candidate identified in prior evaluations of 22 p-block elements. Using density functional theory (DFT) methods, we studied the adsorption behavior of 9 probe molecules: N2O, NO2, NO, N2, CO2, CO, O2, H2O, and H2. Four distinct adsorption behaviors were identified: (i) dissociation of NO2, O2, and H2, (ii) substitution of B by N for NO, (iii) chemisorption of N2O, CO, and H2O, and (iv) physisorption of N2 and CO2. These interactions are driven by the bonding affinity with boron and geometrical constraints of the sheet. The enhanced reactivity of B-MoTe2 arises from boron adopting more favorable orbital hybridization during molecule adsorption, yielding adsorption strengths tens of times higher than those in pristine MoTe2, where interactions are dominated by van der Waals forces. The unique physicochemical properties of B-MoTe2 highlight the potential for tailored reactivity in catalysis and sensing applications and provide a foundational framework for developing effective doping strategies in TMD-based materials.

7456 - 7470

10.1021/acs.jpcc.5c00072

https://doi.org/10.1021/acs.jpcc.5c00072

CC BY (attribution alone)

open journal

final published version

at the time of publication

140