The electrosynthesis from 5‐hydroxymethylfurfural (HMF) is considered a green strategy to achieve biomass‐derived high‐value chemicals. As the molecular structure of HMF is relatively complicated, understanding the HMF adsorption/catalysis behavior on electrocatalysts is vital for biomass‐based electrosynthesis. The electrocatalysis behavior can be modulated by tuning the adsorption energy of the reactive molecules. In this work, the HMF adsorption behavior on spinel oxide, Co3O4 is discovered. Correspondingly, the adsorption energy of HMF on Co3O4 is successfully tuned by decorating with single‐atom Ir. It is observed that compared with bare Co3O4, single‐atom‐Ir‐loaded Co3O4 (Ir‐Co3O4) can enhance adsorption with the CC groups of HMF. The synergetic adsorption can enhance the overall conversion of HMF on electrocatalysts. With the modulated HMF adsorption, the as‐designed Ir‐Co3O4 exhibits a record performance (with an onset potential of 1.15 VRHE) for the electrosynthesis from HMF.
The development of atomically precise dinuclear heterogeneous catalysts is promising to achieve efficient catalytic performance and is also helpful to the atomic-level understanding on the synergy mechanism under reaction conditions. Here, we report a Ni 2 (dppm) 2 Cl 3 dinuclear-cluster-derived strategy to a uniform atomically precise Ni 2 site, consisting of two Ni 1 −N 4 moieties shared with two nitrogen atoms, anchored on a N-doped carbon. By using operando synchrotron X-ray absorption spectroscopy, we identify the dynamically catalytic dinuclear Ni 2 structure under electrochemical CO 2 reduction reaction, revealing an oxygen-bridge adsorption on the Ni 2 −N 6 site to form an O−Ni 2 −N 6 structure with enhanced Ni−Ni interaction. Theoretical simulations demonstrate that the key O−Ni 2 −N 6 structure can significantly lower the energy barrier for CO 2 activation. As a result, the dinuclear Ni 2 catalyst exhibits >94% Faradaic efficiency for efficient carbon monoxide production. This work provides bottom-up target synthesis approaches and evidences the identity of dinuclear sites active toward catalytic reactions.
Single-atom catalysts (SACs) have enormous significance for heterogeneous catalysis. However, understanding how SACs function at molecular level remains as a huge challenge. Here, we report a general approach to anchor...
The electrooxidation of 5‐hydroxymethylfurfural (HMF) offers a promising green route to attain high‐value chemicals from biomass. The HMF electrooxidation reaction (HMFOR) is a complicated process involving the combined adsorption and coupling of organic molecules and OH− on the electrode surface. An in‐depth understanding of these adsorption sites and reaction processes on electrocatalysts is fundamentally important. Herein, the adsorption behavior of HMF and OH−, and the role of oxygen vacancy on Co3O4 are initially unraveled. Correspondingly, instead of the competitive adsorption of OH− and HMF on the metal sites, it is observed that the OH− can fill into oxygen vacancy (Vo) prior to couple with organic molecules through lattice oxygen oxidation reaction process, which could accelerate the rate‐determining step of the dehydrogenation of 5‐hydroxymethyl‐2‐furancarboxylic acid (HMFCA) intermediates. With the modulated adsorption sites, the as‐designed Vo‐Co3O4 shows excellent activity for HMFOR with the earlier potential of 90 and 120 mV at 10 mA cm−2 in 1 m KOH and 1 m PBS solution. This work sheds insight on the catalytic mechanism of oxygen vacancy, which benefits designing a novel electrocatalysts to modulate the multi‐molecules combined adsorption behaviors.
Dual-metal-site catalysts (DMSCs) are emerging as a new frontier in the field of oxygen reduction reaction (ORR). However, there is a lack of design principles to provide a universal description of the relationship between intrinsic properties of DMSCs and the catalytic activity. Here, we identify the origin of ORR activity and unveil design principles for graphene-based DMSCs by means of density functional theory computations and machine learning (ML). Our results indicate that several experimentally unexplored DMSCs can show outstanding ORR activity surpassing that of platinum. Remarkably, our ML study reveals that the ORR activity of DMSCs is intrinsically governed by some fundamental factors, such as electron affinity, electronegativity, and radii of the embedded metal atoms. More importantly, we propose predictor equations with acceptable accuracy to quantitatively describe the ORR activity of DMSCs. Our work will accelerate the search for highly active DMSCs for ORR and other electrochemical reactions.
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