Modulating electronic structure of CoP electrocatalysts towards enhanced hydrogen evolution by Ce chemical doping in both acidic and basic media

et al. 2019

Advanced Science

The design of MoS 2 ‐based electrocatalysts with exceptional reactivity and robustness remains a challenge due to thermodynamic instability of active phases and catalytic passiveness of basal planes. This study details a viable in situ reconstruction of zinc–nitrogen coordinated cobalt–molybdenum disulfide from structure directing metal–organic framework (MOF) to constitute specific heteroatomic coordination and surface ligand functionalization. Comprehensive experimental spectroscopic studies and first‐principle calculations reveal that the rationally designed electron‐rich centers warrant efficient charge injection to the inert MoS 2 basal planes and augment the electronic structure of the inactive sites. The zinc–nitrogen coordinated cobalt–molybdenum disulfide shows exceptional catalytic activity and stability toward the hydrogen evolution reaction with a low overpotential of 72.6 mV at −10 mA cm −2 and a small Tafel slope of 37.6 mV dec −1 . The present study opens up a new opportunity to stimulate catalytic activity of the in‐plane MoS 2 basal domains for enhanced electrochemistry and redox reactivity through a “molecular reassembly‐to‐heteroatomic coordination and surface ligand functionalization” based on highly adaptable MOF template.

Section: Doi: 101002/advs201900140mentioning

confidence: 65%

Section: Doi: 101002/advs201900140mentioning

confidence: 99%

Stimulated Electrocatalytic Hydrogen Evolution Activity of MOF‐Derived MoS₂ Basal Domains via Charge Injection through Surface Functionalization and Heteroatom Doping

Yilmaz

et al. 2019

Advanced Science

“…As expected, 8.3% Zn doped CoP showed promoted HER activity with merely requiring 39 mV overpotential to drive a current density of 10 mA cm −2 , which was better than that of pristine CoP (82 mV), Zn 0.04 Co 0.96 P (46 mV) and Zn 0.13 Co 0.87 P (66 mV) (Figure c). Beyond Zn, elements of Mn, V, Ce, Cu, Cr were successively recognized as good dopants . The enhanced performance was ascribed to the enhanced electron interaction and optimized Δ G H* .…”

Section: Modulated Strategies For Tmps In Electrocatalytic Her Oer mentioning

confidence: 99%

Multifunctional Transition Metal‐Based Phosphides in Energy‐Related Electrocatalysis

Advanced Energy Materials

Dong

Jiao

2019

387

220

The exploitation of cheap and efficient electrocatalysts is the key to make energy‐related electrocatalytic techniques commercially viable. In recent years, transition metal phosphides (TMPs) electrocatalysts have gained a great deal of attention owing to their multifunctional active sites, tunable structure, and composition, as well as unique physicochemical properties. This review summarizes the up‐to‐date progress on TMPs in energy‐related electrocatalysis from diversified synthetic methods, ingenious‐modulated strategies, and novel applications. In order to set forth theory–structure–performance relationships upon TMPs, the corresponding reaction mechanisms, electrocatalytsts' structure/composition designs and desired electrochemical performance are jointly discussed, along with demonstrating their practical electrocatalytic applications in overall water splitting, metal–air batteries, lithium–sulfur batteries, etc. In the end, some underpinning issues and research orientations of TMPs toward efficient energy‐related electrocatalysis are briefly proposed.

“…[52,53] The TOF of the MoS 2 -3 was calculated based on previous reports by electrochemically quantifying the active sites using PBS (1 m)w ith pH 7a nd the scan rate of 100 mV s À1 . [53] The CV cycles and the polarization curves, which are normalized for the active sites, expressed in terms of turnover frequency are shown in Figure S8, Supporting Information. The value of TOF obtained is 0.29 S À1 at overpotential À0.2V .…”

Section: Resultsmentioning

confidence: 99%

Activating the MoS₂ Basal Plane by Controllable Fabrication of Pores for an Enhanced Hydrogen Evolution Reaction

Geng

Liu

et al. 2018

Chemistry A European J

Molybdenum disulfide has drawn persistent interest as a promising nonprecious electrocatalyst alternative to Pt for the hydrogen evolution reaction (HER). However, the MoS2 catalytic efficiency is still lower than the Pt‐based catalysts owing to insufficient active sites with more inert basal planes. Herein, we designed and synthesized porous MoS2 nanosheets to activate the basal planes by etching away Al in Al‐doped MoS2. The optimized porous MoS2 shows a small onset overpotential as low as 136 mV, a large cathode current density of 10 mA cm−2 at η=201 mV, a low Tafel slope of 62 mV decade−1, and a high TOF of 0.29 H2 s−1 per active site at η=200 mV. This study opens up new avenues for designing electrocatalysts based on porous MoS2 or other layered materials with enhanced HER performance.