Interstitial boron-triggered electron-deficient Os aerogels for enhanced pH-universal hydrogen evolution

Abstract

Developing high-performance electrocatalysts for hydrogen evolution reaction (HER) is crucial for sustainable hydrogen production, yet still challenging. Here, we report boron-modulated osmium (B-Os) aerogels with rich defects and ultra-fine diameter as a pH-universal HER electrocatalyst. The catalyst shows the small overpotentials of 12, 19, and 33 mV at a current density of 10 mA cm−2 in acidic, alkaline, and neutral electrolytes, respectively, as well as excellent stability, surpassing commercial Pt/C. Operando X-ray absorption spectroscopy shows that interventional interstitial B atoms can optimize the electron structure of B-Os aerogels and stabilize Os as active sites in an electron-deficient state under realistic working conditions, and simultaneously reveals the HER catalytic mechanisms of B-Os aerogels in pH-universal electrolytes. The density functional theory calculations also indicate introducing B atoms can tailor the electronic structure of Os, resulting in the reduced water dissociation energy and the improved adsorption/desorption behavior of hydrogen, which synergistically accelerate HER.

P-modified hollow carbon mesoporous nanospheres decorated with ultrafine OsP alloy nanoparticles for nonacidic hydrogen evolution

“…4e, because of the p-band matching, P 2p orbital shows a strong localization for bonding with O 2p orbital of water and hydroxyl groups, 47 and thus the phosphorus species can facilitate the water dissociation process (Volmer step). 48 Moreover, the positive shift of the Os 4f peak caused by phosphorus doping can induce the downshift of the d-band center, 49 which can decrease hydrogen adsorption energy on catalysts and thus optimize the Os–H ads interaction (Tafel step), 50 resulting in the facilitated formation of hydrogen.…”

Processable Conjugated Microporous Polymer Gels and Monoliths: Fundamentals and Versatile Applications

“…In terms of potential applications, compared to other widely reported materials, − the multifunctional CMP gels and monoliths with careful design display promising prospects for widespread applications including gas separation, electrochromic devices, and energy storage. ,, Clinically, the injection of specific hydrogels into the body is an ideal method for drug delivery to target cells. ,− For this regard, the CMP gels serve as a powerful platform to conjugate components with specific biological functions into hydrogel networks and effectively control the release rate and immune irritation of vaccines. ,,, For heterogeneous catalysis, with the help of powerful polymerization tools, different catalysis active molecules such as metalloporphyrin, ,,, binol-derived phosphoric acid, , Trőger’s base, , and N-heterocyclic carbene can be introduced into the reconstructed 3D CMP conjugated networks for specific chemical applications. In addition, in the field of hydrogels and energy applications, ,,− the CMP gels and monoliths with binding sites can tightly bind conductive materials for broad application prospects.…”

Boron-Doped Platinum-Group Metals in Electrocatalysis: A Perspective

“…31 On the other hand, the electron transfer and/or orbital hybridization between the PGM and the interstitial dopant manifest a delicate control on the surface electronic structure of the resulting catalysts. 32,33 Among the light-element-doped PGM catalysts, B-doped PGMs were historically once studied in the thermocatalytic alkyne hydrogenation reactions. 34−36 In 2009, our group came up with the first report 37 on electrocatalysis of the formic acid oxidation reaction (FAOR) on homesynthesized Pd−B/C catalysts with improved electrocatalytic activity and anti-CO-poisoning stability.…”