CoP‐Doped MOF‐Based Electrocatalyst for pH‐Universal Hydrogen Evolution Reaction

Abstract

Although electrocatalysts based on transition metal phosphides (TMPs) with cationic/anionic doping have been widely studied for hydrogen evolution reaction (HER), the origin of performance enhancement still remains elusive mainly due to the random dispersion of dopants.H erein, we report ac ontrollable partial phosphorization strategy to generate CoP species within the Co-based metal-organic framework (Co-MOF). Density functional theory calculations and experimental results reveal that the electron transfer from CoP to Co-MOF through N-P/N-Co bonds could lead to the optimizedadsorption energy of H 2 O(DG H 2 O * )a nd hydrogen (DG H* ), which, together with the unique porous structure of Co-MOF,c ontributes to the remarkable HER performance with an overpotential of 49 mV at ac urrent density of 10 mA cm À2 in 1m phosphate buffer solution (PBS,p H7.0). The excellent catalytic performance exceeds almost all the documented TMP-based and non-noble-metal-based electrocatalysts.I na ddition, the CoP/Co-MOF hybrid also displays Pt-like performance in 0.5 m H 2 SO 4 and 1m KOH, with the overpotentials of 27 and 34 mV,r espectively,a tacurrent density of 10 mA cm À2 .

Co/CoP Nanoparticles Encapsulated Within N, P-Doped Carbon Nanotubes on Nanoporous Metal-Organic Framework Nanosheets for Oxygen Reduction and Oxygen Evolution Reactions

“…As a general precursor for the preparation of TMPs, MOFs compounds have been extensively studied by reason of their large specific surface area, high porosity, and structural coordination [40,41]. In general, MOFs carbonization process requires high temperature calcination, which will damage the original MOFs structure and cause agglomeration of the metal center [42]. Direct use of MOFs as an electrocatalyst can utilize its good structure, but their stability is relatively low, and catalytic activity is poor, especially under strong alkaline and acidic solution conditions [43,44].…”

Modulating Electronic Structure of Metal-Organic Frameworks by Introducing Atomically Dispersed Ru for Efficient Hydrogen Evolution

“…5c, Ru in NiRu 0.13 -BDC shows much lower adsorption energy of H 2 O (ΔG H2O* ) compared with Ni in Ni-BDC and NiRu 0.13 -BDC, indicating the strongest water adsorption, which bene ts for the following step to generate adsorbed H atoms. [65,66] In addition, ΔG H* is often used as one of the key descriptors to predict and evaluate the activity for HER on catalyst surface and the promising catalysts should possess thermoneutral ΔG H* . [67] Interestingly, the ΔG H* of Ni in NiRu 0.13 -BDC (Fig.…”

“…All the calculations are performed in the framework of the density functional theory with the projector augmented plane-wave method, as implemented in the Vienna ab initio simulation package. [66] The generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof is selected for the exchange-correlation potential. [67] The cut-off energy for plane wave is set to 400 eV.…”

Bio-inspired general synthesis of superplastic metal-organic framework aerogels and their applications

“…As we know, exible energy systems have attracted considerable interest because of their remarkable properties such as small-size unit, lightweight, and shape conformability, which are promising components for versatile portable, foldable, and wearable devices. 16,[28][29][30] However, the currently reported hydrogen evolution systems are generally fabricated in the form of bulky and heavy architectures, indicating that they are far behind the requirement of exibility. Conventional electrodes are synthesized by depositing of powder or thin-lm form electrocatalysts, such as MOFs and others, [31][32][33] onto rigid substrates (like glassy carbon 31,32 and FTO glass 33 ), only resulting in bulk and fragile electrolytic devices.…”

“…Conventional electrodes are synthesized by depositing of powder or thin-lm form electrocatalysts, such as MOFs and others, [31][32][33] onto rigid substrates (like glassy carbon 31,32 and FTO glass 33 ), only resulting in bulk and fragile electrolytic devices. Very recently, several soft current collectors (such as carbon-ber paper 30 and metal foams 16,28 ) have been employed to make HER catalyst electrodes by taking advantages of their excellent properties of high electrical conductivity, interconnected porous networks, and mechanical robust. Integrating these soft substrates with catalytic active species has been achieved by the synthetic strategies of solution-casting or direct growth.…”