Electronic Modulation of Metal‐Organic Frameworks Caused by Atomically Dispersed Ru for Efficient Hydrogen Evolution

Abstract

Designing excellent electrocatalysts for the hydrogen evolution reaction (HER) is extremely significant in producing clean and sustainable hydrogen fuel. Herein, a rational strategy is developed to fabricate a promising electrocatalyst by introducing atomically dispersed Ru into a cobalt‐based metal‐organic framework (MOF), Co‐BPDC (Co(bpdc)(H2O)2, BPDC: 4,4'‐Biphenyldicarboxylic acid). The obtained CoRu‐BPDC nanosheet arrays exhibit remarkable HER performance with an overpotential of 37 mV at a current density of 10 mA cm−2 in alkaline media, which is superior to most of the MOF‐based electrocatalysts and comparable to the commercial Pt/C. Synchrotron radiation‐based X‐ray absorption fine structure (XAFS) spectroscopy studies verify that the isolated Ru atoms are dispersed in Co‐BPDC nanosheets with the formation of five‐coordinated Ru‐O5 species. XAFS spectroscopy combined with density functional theory (DFT) calculations unravels that atomically dispersed Ru can modulate the electronic structure of the as‐obtained Co‐BPDC, contributing to the optimization of binding strength for H* and the enhancement of HER performance. This work opens a new avenue to rationally design highly‐active single‐atom modified MOF‐based HER electrocatalysts via modulating electronic structures of MOF.

Ultrathin Fe-MOFs modified by Fe9S10 for highly efficient oxygen evolution reaction

“…The charge transfer resistance had an inverse relationship with the size of semicircle. 42 The semicircle of Fe 9 S 10 /Fe-MOF/NF-2 was the smallest, indicating the transfer rate of Fe 9 S 10 /Fe-MOF/NF-2 was the fastest in the OER process (Fig. 4c).…”

Ultrafine Iridium Nanoparticles Anchored on Co-Based Metal–Organic Framework Nanosheets for Robust Hydrogen Evolution in Alkaline Media

“…31 Similarly, Ni et al improved the electronic structure of pristine MOFs by incorporating atomically dispersed Ru into carbon cloth-supported Co-BPDC, enhancing HER performance. 32 It should be noted that the precious metal content of these loads is usually very high, and some even reach 30%.…”

“…For instance, Li and co-workers enhanced a Ni-MOF nanoarray by depositing ruthenium (Ru) nanoparticles (NPs), achieving excellent HER activity and long-term stability across a wide range of pH values . Similarly, Ni et al improved the electronic structure of pristine MOFs by incorporating atomically dispersed Ru into carbon cloth-supported Co-BPDC, enhancing HER performance . It should be noted that the precious metal content of these loads is usually very high, and some even reach 30%.…”

Tailoring the electronic environment of MoSe2via cation metal doping for the enhanced alkaline hydrogen evolution reaction

“…9 Nevertheless, the scarcity and their precious nature would inevitably preclude their large-scale implementation in electrocatalysis. 10–16 Therefore, it is necessary to promote highly active and cost-effective non-precious metal alkaline HER electrocatalysts as alternatives for green hydrogen production. 17–20…”