Tailoring Electronic Structure of NbB2 Nanorods Through Selenium Incorporation for Synergistically Enhanced Hydrogen Evolution and Triboelectric Energy Harvesting

Abstract

ABSTRACT The sluggish hydrogen evolution reaction (HER) kinetics of non‐noble‐metal catalysts remain a major challenge for efficient hydrogen production. Herein, selenium‐doped niobium diboride (Se‐NbB 2 ) nanorods were synthesized via a molten‐salt‐assisted route followed by microwave‐assisted treatment, yielding a catalyst with higher conductivity and superior electrocatalytic performance. HER activity reveals that Se‐NbB 2 exhibits excellent performance, requiring an overpotential of only 147 mV to achieve 10 mA cm − 2 and maintaining stable operation for more than 6 days under alkaline conditions. Furthermore, the catalyst demonstrates efficient bifunctional water‐splitting performance, delivering 10 mA cm − 2 at a cell voltage of 1.79 V. First‐principles calculations reveal that Se incorporation modulates the electronic structure of NbB 2 by shifting the Nb d‐band center upward and improving electrical conductivity, thereby optimizing hydrogen adsorption free energy toward thermoneutral conditions and accelerating HER kinetics. Beyond electrocatalysis, Se‐NbB 2 was employed as an electrode material in a triboelectric nanogenerator (TENG), generating a maximum output voltage of 703 V and a current of 33 µA. The enhanced catalytic and triboelectric performances are attributed to improved conductivity and charge‐transport characteristics induced by selenium incorporation. This work highlights heteroatom‐mediated electronic‐structure engineering as an effective strategy for developing multifunctional transition‐metal boride materials for sustainable energy conversion, hydrogen generation, and energy‐harvesting technologies.