RESUMO
Two-electron oxygen reduction reaction (2e- ORR) is a promising method for the synthesis of hydrogen peroxide (H2O2). However, high energy barriers for the generation of key *OOH intermediates hinder the process of 2e- ORR. Herein, we prepared a copper-supported indium selenide catalyst (Cu/In2Se3) to enhance the selectivity and yield of 2e- ORR by employing an electronic metal-support interactions (EMSIs) strategy. EMSIs-induced charge rearrangement between metallic Cu and In2Se3 is conducive to *OOH intermediate generation, promoting H2O2 production. Theoretical investigations reveal that the inclusion of Cu significantly lowers the energy barrier of the 2e- ORR intermediate and impedes the 4e- ORR pathway, thus favoring the formation of H2O2. The concentration of H2O2 produced by Cu/In2Se3 is ~2â times than In2Se3, and Cu/In2Se3 shows promising applications in antibiotic degradation. This research presents a valuable approach for the future utilization of EMSIs in 2e- ORR.
RESUMO
Recognizing the essential factor governing interfacial hydrogen/oxygen evolution reactions (HER/OER) is central to electrocatalytic water-splitting. Traditional strategies aiming at enhancing electrocatalytic activities have mainly focused on manipulating active site valencies or coordination environments. Herein, the role of interfacial adsorption is probed and modulated by the topological construct of the electrocatalyst, a frequently underestimated non-Faradaic mechanism in the dynamics of electrocatalysis. The engineered Co0.75Fe0.25P nanorods, anchored with FeOx clusters, manifest a marked amplification of the surface electric field, thus delivering a substantially improved bifunctional electrocatalytic performance. In alkaline water splitting anion exchange membrane (AEM) electrolyzer, the current density of 1.0 A cm-2 can be achieved at a cell voltage of only 1.73 V for the FeOx@Co0.75Fe0.25P|| FeOx@Co0.75Fe0.25P pairs for 120 h of continuous operation at 1.0 A cm-2. Detailed investigations of electronic structures, combined with valence state and coordination geometry assessments, reveal that the enhancement of catalytic behavior in FeOx@Co0.75Fe0.25P is chiefly attributed to the strengthened adsorptive interactions prompted by the intensified electric field at the surface. The congruent effects observed in FeOx-cluster-decorated Co0.75Fe0.25P nanosheets underscore the ubiquity of this effect. The results put forth a compelling proposition for leveraging interfacial charge densification via deliberate cluster supplementation.
RESUMO
Thermoset elastomers have been extensively applied in many fields because of their excellent mechanical strengths and durable characteristics, such as an excellent chemical resistance. However, in the context of environmental issues, the nonrecyclability of thermosets has become a major barrier to the further development of these materials. Here, a well-tailored strategy is reported to solve this problem by introducing mismatched supramolecular interactions (MMSIs) into a covalently cross-linked poly(urethane-urea) network with dynamic acylsemicarbazide moieties. The MMSIs significantly strengthen and toughen the thermoset elastomer by effectively dissipating energy and resisting external stress. In addition, the elastomer recycling efficiency is improved 2.7-fold due to the superior reversibility of the MMSIs. The optimized thermoset elastomer features outstanding characteristics, including an ultrahigh tensile strength (110.8 MPa), an unprecedented tensile toughness (1245.2 MJ m-3), as well as remarkable resistance to chemical media, creep, and damage. Most importantly, it exhibits an extraordinary multirecyclability, and the 4th recycling efficiency remains close to 100%. This scalable method promotes the development of thermosets with both high performance and excellent recyclability, thereby providing valuable guidance for addressing the issue of nonrecyclability from a molecular design standpoint.