Enhanced hydrogen evolution reaction on hybrids of cobalt phosphide and molybdenum phosphide

Fang, Si-Ling; Chou, Tsu‐Chin; Samireddi, Satyanarayana; Chen, Kuei‐Hsien; Chen, Li‐Chyong; Chen, Wei-Fu

doi:10.1098/rsos.161016

Cited by 17 publications

(9 citation statements)

References 41 publications

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“…However, this method currently accounts for ∼4% of the worldwide hydrogen production because of the high cost of noble metal catalysts . Therefore, earth-abundant transition metals and their alloys (Ni, − Ni–Fe, Ni–Co, Co–Mo) as well as transition-metal phosphides (TMPs), , nitrides, carbides, and chalcogenides − are being investigated as low-cost, earth-abundant electrocatalysts for sustainable hydrogen generation technologies.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Activity of Bimetallic Ni–Mo–P Nanocrystals for Hydrogen Evolution Reaction

Eladgham

Rodene

Sarkar

et al. 2020

ACS Appl. Nano Mater.

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Electrochemical water splitting represents a sustainable method to produce molecular hydrogen, a foreseeable clean energy alternative to exhaustible fossil fuels. Transition-metal phosphides (TMPs) are emerging as earth-abundant catalysts for water splitting, and their activity can be further improved by incorporation of synergetic metals to produce bimetallic TMP catalysts. Herein, two distinct colloidal chemistry methods were developed to produce discrete nickel molybdenum phosphide (Ni−Mo−P) nanoparticles (NPs) that show varying crystal structures, morphologies, and compositions as alkaline hydrogen evolution reaction (HER) catalysts. The one-pot route produced smaller homogeneous NPs, ranging from 4 to 11 nm, with a nearspherical morphology. The two-pot synthesis resulted in larger heterogeneous NPs, ranging from ∼50 to 80 nm, with a polygonal morphology. Both nanostructures show either a hexagonal Ni 2 P or tetragonal Ni 12 P 5 crystal structure and a shift in X-ray diffraction patterns to lower 2θ angles, consistent with the formation of bimetallic TMPs. The X-ray photoelectron spectra indicate the presence of partially charged core species (Ni δ+ , Mo δ+ , and P δ− ) as well as minor higher valent (Ni n+ , Mo n+ , and PO 4 3− , n ≥ 2) surface species, presumably bound to surfactant ligands and/or oxides. Among heterogeneous and homogeneous NPs investigated, the hexagonal Ni 2−x Mo x P NPs show lower overpotentials (i.e., high HER activity) in comparison to tetragonal Ni 12−x Mo x P 5 NPs. The HER activity of both nanostructures follows a mixed Volmer− Heyrovsky reaction mechanism consistent with Tafel slopes of 49.5−100.6 mV/dec. The homogeneous and heterogeneous Ni 1.87 Mo 0.13 P NPs showed the lowest overpotentials of 101 and 96 mV, respectively, and outperformed both hexagonal Ni 2 P (156 mV) and tetragonal Ni 12−x Mo x P (198 mV) NPs at a current density of −10 mA/cm 2 . This work provides insights into the design and synthesis of high-efficiency TMP nanostructures for alkaline HER studies.

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Section: Introductionmentioning

confidence: 99%

Electrocatalytic Activity of Bimetallic Ni–Mo–P Nanocrystals for Hydrogen Evolution Reaction

Eladgham

Rodene

Sarkar

et al. 2020

ACS Appl. Nano Mater.

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“…Their elemental makeup is generally denoted as MX 2 , where M is a transition metal and X is a chalcogen, ,, and they have fascinating research interest owing to their abundance and superior HER electrochemical activity . Previous studies have shown that TMDCs have tunable electronic structure which can enhance their intrinsic HER electrochemical properties to provide efficient catalysts. − In particular, nanocrystalline TMDC structures are having exposed sulfur or selenide edge sites to catalyze the hydrogen evolution rather than the inert bulk form. , …”

Section: Introductionmentioning

confidence: 99%

Improved Hydrogen Evolution Reaction Performance using MoS₂–WS₂ Heterostructures by Physicochemical Process

Vikraman

Hussain

Akbar

et al. 2018

ACS Sustainable Chem. Eng.

118

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This report describes the synthesis of a layered molybdenum disulfide (MoS2)–tungsten disulfide (WS2) heterostructure onto fluorine doped tin oxide covered glass substrates using a combination of chemical bath deposition and RF sputtering techniques. FESEM images revealed that the MoS2–WS2 heterostructure surface consisted of a cauliflower structured array of grains with spherical structures. The vertically aligned atomic layers were explored by transmission electron microscopy images for MoS2–WS2 heterostructure. Hydrogen evolution reaction (HER) kinetics show overpotentials of 151 and 175 mV @ 10 mA/cm2 with Tafel slope values of 90 and 117 mV/decade for pristine MoS2 and WS2 electrocatalysts, respectively. Improved electrocatalytic activity for HER was established with overpotential 129 mV @ 10 mA/cm2 and Tafel slope 72 mV/decade for the MoS2–WS2 heterostructure. The MoS2–WS2 heterostructure electrocatalyst showed robust continuous HER performance over 20 h in an acidic solution. This improved electrochemical performance emerges from the elevation of electron–hole separation at the layer interfaces and sharing of active edge sites through the interface. This study provides the basis to develop new applications for transition-metal dichalcogenides heterostructures in future energy conversion systems.

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“…Both the Co-and Ni-incorporated MoP samples exhibited the highest catalytic activities among the samples reacted for 1.5 hours, sharing the same trends as their geometrical area-normalized polarization curves. Recent studies have reported a volcano-shaped relationship between HER performance and the ratio of metal species in a bimetallic TMP 34,58 ; the excessive addition of dopant metal cations inhibits NP catalytic activity. The extended reaction time did not necessarily improve electrocatalytic activity due to NP agglomeration and compositional changes.…”

Section: Resultsmentioning

confidence: 99%

Transition‐metal‐incorporated molybdenum phosphide nanocatalysts synthesized through post‐synthetic transformation for the hydrogen evolution reaction

Kim

Park

Lee

et al. 2022

Intl J of Energy Research

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Summary Post‐synthetic chemical transformation is a recently emerging nanomaterial manufacturing method for obtaining materials with precisely modulated properties. Through post‐synthetic transformation methods, foreign elements are exchanged or incorporated into presynthesized nanoparticles (NPs). However, metal phosphides have not been primarily used as starting materials because of their strong bonding characteristics. In this study, we synthesized bimetallic transition metal phosphide (TMP) NPs through a cation addition reaction using amorphous molybdenum phosphide (MoP) as the starting material, which is a promising catalyst for the hydrogen evolution reaction (HER). The additional metal elements, namely Co and Ni, were successfully incorporated into the parent MoP NPs, which led to only marginal changes in size or shape, even after 12 hours of reaction. Because morphological factors strongly influence catalytic activity, nanocatalysts with identical morphologies provide a direct comparison among NPs with various chemical properties. The Co‐ and Ni‐incorporated MoP NPs exhibited significantly enhanced catalytic activities for the HER, with similar electrochemically active surface areas. In particular, Co‐1.5 h‐MoP showed the highest HER activity (167 mV at −10 mA cm−2) and durability among the samples in 0.5 M H2SO4. Such an improvement in catalytic activity through the cation addition reaction may be ascribed to the difference in the electronegativities of the original and newly added metal cations, as confirmed by X‐ray photoelectron spectroscopy (XPS), resulting in abundant metal‐P bonding and oxidation resistivity. This study provides a new advanced platform for directly analyzing the inherent characteristics of nanomaterials for diverse applications, especially electrocatalysis.

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Enhanced hydrogen evolution reaction on hybrids of cobalt phosphide and molybdenum phosphide

Cited by 17 publications

References 41 publications

Electrocatalytic Activity of Bimetallic Ni–Mo–P Nanocrystals for Hydrogen Evolution Reaction

Electrocatalytic Activity of Bimetallic Ni–Mo–P Nanocrystals for Hydrogen Evolution Reaction

Improved Hydrogen Evolution Reaction Performance using MoS₂–WS₂ Heterostructures by Physicochemical Process

Transition‐metal‐incorporated molybdenum phosphide nanocatalysts synthesized through post‐synthetic transformation for the hydrogen evolution reaction

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Enhanced hydrogen evolution reaction on hybrids of cobalt phosphide and molybdenum phosphide

Cited by 17 publications

References 41 publications

Electrocatalytic Activity of Bimetallic Ni–Mo–P Nanocrystals for Hydrogen Evolution Reaction

Electrocatalytic Activity of Bimetallic Ni–Mo–P Nanocrystals for Hydrogen Evolution Reaction

Improved Hydrogen Evolution Reaction Performance using MoS2–WS2 Heterostructures by Physicochemical Process

Transition‐metal‐incorporated molybdenum phosphide nanocatalysts synthesized through post‐synthetic transformation for the hydrogen evolution reaction

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Improved Hydrogen Evolution Reaction Performance using MoS₂–WS₂ Heterostructures by Physicochemical Process