Substituting hydrazine oxidation reaction for oxygen evolution reaction can result in greatly reduced energy consumption for hydrogen production, however, the mechanism and the electrochemical utilization rate of hydrazine oxidation reaction remain ambiguous. Herein, a bimetallic and hetero-structured phosphide catalyst has been fabricated to catalyze both hydrazine oxidation and hydrogen evolution reactions, and a new reaction path of nitrogen-nitrogen single bond breakage has been proposed and confirmed in hydrazine oxidation reaction. The high electro-catalytic performance is attributed to the instantaneous recovery of metal phosphide active site by hydrazine and the lowered energy barrier, which enable the constructed electrolyzer using bimetallic phosphide catalyst at both sides to reach 500 mA cm⁻² for hydrogen production at 0.498 V, and offer an enhanced hydrazine electrochemical utilization rate of 93%. Such an electrolyzer can be powered by a bimetallic phosphide anode-equipped direct hydrazine fuel cell, achieving self-powered hydrogen production at a rate of 19.6 mol h⁻¹ m⁻².

Although the CoSb₃-based skutterudite thermoelectric devices have been highly expected for wide uses such as waste heat recovery and space power supply, the limited long-term service stability majorly determined by the degradation of electrode interface obstructs its applications. Here, we built up an effective criterion for screening barrier layer based on the combination of negative interfacial reaction energy and high activation energy barrier of Sb migration through the formed interfacial reaction layer. Accordingly, we predicted niobium as a promising barrier layer. The experimental results show the skutterudite/Nb joint has the slowest interfacial reaction layer growth rate and smallest interfacial electrical resistivity. The fabricated 8-pair skutterudite module using Nb as barrier layer achieves a recorded conversion efficiency of 10.2% at hot-side temperature of 872 K and shows excellent stability during long-time aging. This simple criterion provides an effective guidance on screening barrier layer with bonding-blocking-conducting synergetic functions for thermoelectric device integration.

Unsatisfied electrode bonding in half-Heusler devices renders thermal damage and large efficiency loss, which limits their practical service at high temperatures. Here, we develop a thermodynamic strategy to screen barrier layer elements. Theoretically, we found that the interface between VIIB elements and half-Heuslers possesses near-zero interfacial reaction energy and large atomic diffusion barrier. Experimentally, such an interphase proves to be the atomic direct bonding and has high thermal stability at 1073 K, leading to ideal ohmic contact. Such thermally inert and ohmic contact interface enable modules stably to work at elevated temperature up to 1100 K, which releases the peak performance of half-Heuslers and in turn boosts the energy conversion efficiencies to the records of 11.1% and 13.3% for half-Heusler single-stage and half-Heusler/Bi₂Te₃ segmented modules. This design strategy provides a feasible solution for the high-temperature half-Heusler generators and gives enlightenment for other package interconnection design of electronic devices.