Boron‐Induced Electronic‐Structure Reformation of CoP Nanoparticles Drives Enhanced pH‐Universal Hydrogen Evolution

Abstract

Even though transition‐metal phosphides (TMPs) have been developed as promising alternatives to Pt catalyst for the hydrogen evolution reaction (HER), further improvement of their performance requires fine regulation of the TMP sites related to their specific electronic structure. Herein, for the first time, boron (B)‐modulated electrocatalytic characteristics in CoP anchored on the carbon nanotubes (B‐CoP/CNT) with impressive HER activities over a wide pH range are reported. The HER performance surpasses commercial Pt/C in both neutral and alkaline media at large current density (>100 mA cm−2). A combined experimental and theoretical study identified that the B dopant could reform the local electronic configuration and atomic arrangement of bonded Co and adjacent P atoms, enhance the electrons’ delocalization capacity of Co atoms for high electrical conductivity, and optimize the free energy of H adsorption and H2 desorption on the active sites for better HER kinetics.

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

“…Figure 5f shows the d -band center ( ε d ) of Os and Os-2B(I) in the density of states. As expected, the introducing interstitial B atoms lower the ε d of Os down from the Fermi level, manifesting a weaker H adsorption, which is in accordance with the d -band theory 58 , 59 . From the above results, it is believed that constructing B atoms can regulate the electronic configuration of Os, resulting in an improved ΔE B and a more thermoneutral ΔG H* , and thus improve the HER activity.…”

Enhancing Polysulfide Confinement and Electrochemical Kinetics by Amorphous Cobalt Phosphide for Highly Efficient Lithium–Sulfur Batteries

“…The peak at 1.74 Å in rGO-CNT-CoP­(C) spectrum and the peak at 1.65 Å in rGO-CNT-CoP­(A) spectrum are both attributed to Co–P bonds. Compared to rGO-CNT-CoP­(C), the Co–P bond in rGO-CNT-CoP­(A) shifts to a low-R position with a weaker peak intensity, which indicates the shorter Co–P bond length and the more disorder structure of amorphous CoP. − The X-ray photoelectron spectroscopy (XPS) was used to further understand the structural differences between amorphous CoP and crystalline CoP and how CoP interacts with LiPSs. As shown in Figure c,d, the Co 2p 3/2 spectrum of rGO-CNT-CoP­(A) can be deconvoluted into three peaks.…”

Regulating electronic structure of two‐dimensional porous Ni/Ni3N nanosheets architecture by Co atomic incorporation boosts alkaline water splitting

“…27,28 Doping strategy is an efficient approach to tune the dband center and enhance the performance of electrocatalysts. [29][30][31] With the incorporation of guest heteroatoms, the crystal lattices of the host will undergo a subtle change and the d-band center will be downshifted, 30,32,33 thus the electronic surroundings will be precisely regulated at the atomic level and the adsorption/desorption of reactive species is more favorable. [34][35][36] In this case, it raises the question whether it is possible to manipulate the electronic structure of heterojunctions for efficient overall water splitting by incorporation of heteroatoms.…”

“…Doping strategy is an efficient approach to tune the d‐band center and enhance the performance of electrocatalysts 29–31 . With the incorporation of guest heteroatoms, the crystal lattices of the host will undergo a subtle change and the d‐band center will be downshifted, 30,32,33 thus the electronic surroundings will be precisely regulated at the atomic level and the adsorption/desorption of reactive species is more favorable 34–36 .…”