Modulating the electronic environment of single-atom metal catalysts is a promising yet challenging strategy to optimize their catalytic performance. Herein, electron-rich Ru single atoms were successfully confined within a CoOx matrix (Ru0.6CoOx) through a simple manual grinding-reduction strategy. The resulting Ru0.6CoOx catalyst demonstrated exceptional catalytic activity for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF), affording a nearly quantitative DMF yield with an impressive DMF productivity of 210.2 molDMF·mol–1Ru·h–1 at 160 °C. This productivity outperforms most of the noble metal-based catalysts for DMF production. Notably, Ru0.6CoOx also enabled the efficient conversion of HMF to DMF at a low reaction temperature of 120 °C or using a concentrated HMF solution (up to 20 wt %). Experimental studies combined with density functional theory calculations (DFT) revealed that the electronic interaction between the Ru species and CoOx generates electron-rich Ru single atoms, which serve as active sites to boost the H2 activation. Furthermore, the introduction of single Ru atoms was shown to increase the acidity of Ru0.6CoOx, thereby facilitating the cleavage of the C–OH bond during HMF hydrogenolysis. The boosted H2 activation ability and improved acidity of Ru0.6CoOx contribute significantly to its outstanding catalytic performance. This work provides valuable insights into the preparation of electron-rich single-atom metal catalysts for the catalytic hydrodeoxygenation of biomass-derived chemicals.
Wei Jin,Hengbo Wu,Weiquan Cai,Baohua Jia,Munkhbayar Batmunkh,Zexing Wu,Tianyi Ma
Designing highly-efficient and pH-universal electrocatalysts for overall water-splitting reactions is important for the sustainable production of hydrogen. Herein, NiRu nanoparticles encapsulated into N-doped carbon (NiRu@NC) are fabricated with the assistance of MOF for hydrogen evolution reaction (HER) and also evolved into core–shell structured nanomaterials with abundant interfaces for oxygen evolution reaction (OER, Ni/RuOx@C). Benefiting from optimized electronic structure, interfacial synergy effect and special core–shell structure (~150 nm), the newly developed electrocatalysts present remarkable electrocatalytic activities with small overpotentials to drive 10 mA cm −2 for the HER (19 mV in alkaline, 80 mV in neutral, 20 mV in acid) and OER (252 mV, 316 mV, 211 mV). Moreover, the obtained electrocatalysts exhibit outstanding catalytic performances for overall water-splitting in a two-electrode system with 1.53 V and 1.67 V to drive 10 mA cm −2 in basic and neutral electrolyte, respectively. Remarkably, a small potential of 1.47 V is required to deliver 10 mA cm −2 in acidic media and no significant decay of the activity is observed. This work paves the way for designing a novel class of electrocatalyst that can not only exhibit remarkable electrocatalytic water splitting performances in various conditions, but also possess excellent stabilities for future generation of clean energy.
危险品化学品经营许可证（带存储）