Revealing the role of a bridging oxygen in a carbon shell coated Ni interface for enhanced alkaline hydrogen oxidation reaction.

Encapsulating metal nanoparticles inside carbon layers is a promising approach to simultaneously improving the activity and stability of electrocatalysts. The role of carbon layer shells, however, is not fully understood. Herein, we report a study of boron doped carbon layers coated on nickel nanoparticles (Ni@BC), which were used as a model catalyst to understand the role of a bridging oxygen in a carbon shell coated Ni interface for the improvement of the hydrogen oxidation reaction (HOR) activity using an alkaline electrolyte. Combining experimental results and density functional theory (DFT) calculations, we find that the electronic structure of Ni can be precisely tailored by Ni-O-C and Ni-O-B coordinated environments, leading to a volcano type correlation between the binding ability of the OH* adsorbate and HOR activity. The obtained Ni@BC with a optimized d-band center displays a remarkable HOR performance with a mass activity of 34.91 mA mgNi-1, as well as superior stability and CO tolerance. The findings reported in this work not only highlight the role of the OH* binding strength in alkaline HOR but also provide guidelines for the rational design of advanced carbon layers used to coat metal electrocatalysts.

A Highly-Efficient Boron Interstitially Inserted Ru Anode Catalyst for Anion Exchange Membrane Fuel Cells.

Developing high-performance electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the commercialization of anion exchange membrane fuel cells (AEMFCs). Here, boron interstitially inserted ruthenium (B-Ru/C) is synthesized and used as an anode catalyst for AEMFC, achieving a peak power density of 1.37 W cm-2 , close to the state-of-the-art commercial PtRu catalyst. Unexpectedly, instead of the monotonous decline of HOR kinetics with pH as generally believed, an inflection point behavior in the pH-dependent HOR kinetics on B-Ru/C is observed, showing an anomalous behavior that the HOR activity under alkaline electrolyte surpasses acidic electrolyte. Experimental results and density functional theory calculations reveal that the upshifted d-band center of Ru after the intervention of interstitial boron can lead to enhanced adsorption ability of OH and H2 O, which together with the reduced energy barrier of water formation, contributes to the outstanding alkaline HOR performance with a mass activity of 1.716 mA µgPGM -1 , which is 13.4-fold and 5.2-fold higher than that of Ru/C and commercial Pt/C, respectively.

Unveiling the Electrolyte Cations Dependent Kinetics on CoOOH-Catalyzed Oxygen Evolution Reaction.

The electrolyte cations-dependent kinetics have been widely observed in many fields of electrocatalysis, however, the exact mechanism of the influence on catalytic performance is still a controversial topic of considerable discussion. Herein, combined with operando X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), we verify that the electrolyte cations could intercalate into the layer of pristine CoOOH catalyst during the oxygen evolution reaction (OER) process, while the bigger cations lead to enlarged interlayer spacing and increased OER activity, following the order Cs+ >K+ >Na+ >Li+ . X-ray absorption spectroscopy (XAS), in situ Raman, in situ Ultraviolet-visible (UV/Vis) spectroscopy, in situ XAS spectroscopy, cyclic voltammetry (CV), and theoretical calculations reveal that the intercalation of electrolyte cations efficiently modify the oxidation states of Co by enlarging the Co-O bonds, which in turn enhance the d-band center of Co, optimize the adsorption strength of oxygen intermediates, facilitate the formation of OER active Co(IV) species, and reduce the energy barrier of the rate-determing step (RDS), thereby enhancing the OER activity. This work not only provides an informative picture to understand the complicated dependence of OER kinetics on electrolyte cations, but also sheds light on understanding the mechanism of other electrolyte cation-targeted electrocatalysis.

Reconstructured Electrocatalysts during Oxygen Evolution Reaction under Alkaline Electrolytes.

The development of electrocatalysts with high-efficiency and clear structure-activity relationship towards the sluggish oxygen evolution reaction (OER) is essential for the wide application of water electrolyzers. Recently, the dynamic reconstruction phenomenon of the catalysts' surface structures during the OER process has been discovered. With the help of various advanced ex situ and in situ characterization, it is demonstrated that such surface reconstruction could yield actual active species to catalyze the water oxidation process. However, the attention and studies of potential interaction between reconstructed species and substrate are lacking. This review summarizes the recent development of typical reconstructed electrocatalysts and the substrate effect. First, the advanced characterization for electrocatalytic reconstruction is briefly discussed. Then, typical reconstructed electrocatalysts are comprehensively summarized and the key role of substrate effects during the OER process is emphasized. Finally, the future challenges and perspectives of surface reconstructed catalysts for water electrolysis are discussed.

Intermolecular Energy Gap-Induced Formation of High-Valent Cobalt Species in CoOOH Surface Layer on Cobalt Sulfides for Efficient Water Oxidation.

Transition metal-based electrocatalysts will undergo surface reconstruction to form active oxyhydroxide-based hybrids, which are regarded as the "true-catalysts" for the oxygen evolution reaction (OER). Much effort has been devoted to understanding the surface reconstruction, but little on identifying the origin of the enhanced performance derived from the substrate effect. Herein, we report the electrochemical synthesis of amorphous CoOOH layers on the surface of various cobalt sulfides (CoSα ), and identify that the reduced intermolecular energy gap (Δinter ) between the valence band maximum (VBM) of CoOOH and the conduction band minimum (CBM) of CoSα can accelerate the formation of OER-active high-valent Co4+ species. The combination of electrochemical and in situ spectroscopic approaches, including cyclic voltammetry (CV), operando electron paramagnetic resonance (EPR) and Raman, reveals that Co species in the CoOOH/Co9 S8 are more readily oxidized to CoO2 /Co9 S8 than in CoOOH and other CoOOH/CoSα . This work provides a new design principle for transition metal-based OER electrocatalysts.

Efficient Separation of Nucleic Acids with Different Secondary Structures by Metal-Organic Frameworks.

We report the use of metal-organic frameworks (MOFs) for the selective separation of nucleic acids (DNA and RNA) with different secondary structures through size, shape, length, and capability of conformational transition. Three MOFs with precisely controlled pore environments, Co-IRMOF-74-II, -III, and -IV, composed of Co2+ and organic linkers (II, III, and IV), respectively, were used for the inclusion of nucleic acid into their pores from the solution. This was proven to be a spontaneous process from disordered free state to restricted ordered state via circular dichroism (CD) spectroscopy. Three critical factors were identified for their inclusion: (1) size selection induced by steric hindrance, (2) conformation transition energy selection induced by stability, and (3) molecular weight selection. These selection rules were used to extract nucleic acids with flexible and unstable secondary structures from complex mixtures of multiple nucleic acids, leaving those with rigid and stable secondary structures in the mother liquor. This provides the possibility to separate and enrich nucleic acids in bulk through their different structure feature, which is highly desirable in genome-wide structural measurement of nucleic acids. Unlike methods that rely on specific binding antibodies or ligand, this MOF method is capable of selecting all kinds of nucleic acids with similar secondary structure features; therefore, it is suitable for the handling of a large variety and quantity of nucleic acids at the same time. This method also has the potential to gather information about the folding stability of biomolecules with secondary structures.