Morphology controlled synthesis of Pd2Ge nanostructures and their shape-dependent catalytic properties for hydrogen evolution reaction

Chen, Jee-Yee; Jheng, Shao-Lou; Chan, Cheng-Ying

doi:10.1016/j.ijhydene.2019.03.062

Cited by 9 publications

(6 citation statements)

References 47 publications

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“…Germanium is reported for its tendency to form hydrides [ 46 ] in acidic media and promote the HER when incorporated with other active noble metals like ruthenium [ 47 ] and palladium. [ 48 ] Due to the stable formation of GeH [ 49 ] and GeH 2 , [ 50 ] there is an expected enhancement of reaction kinetics of the HER toward making it Volmer–Tafel mechanism resembling Pt. Nonsimilar adjacent atoms can lead to stronger heteroatomic interactions facilitating rapid charge transfer and optimal Metal‐H bond strengths.…”

Section: Resultsmentioning

confidence: 99%

Morphology‐Tuned Pt₃Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

et al. 2022

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compounds. To date, the utilization of nonrenewable energy resources (like coal, petroleum, and natural gas) is exceeding the use of renewable ones like wind, water, biopower, and solar. The enormous growth of population has led to extensive consumption of these fossil fuels [1] and release of noxious CO 2 gas that has caused global warming, hiking the temperature at an alarming rate. Hydrogen (H 2 ) gas, in its molecular form, is the cleanest fuel known to date because its only combusted product is benevolent water. [2] Hydrogen can be used as a fuel in proton exchange membrane fuel cells (PEMFCs) for various routine applications, [3] as a reductant in the utilization of greenhouse gas CO 2 , [4] as a raw material in the production of several chemicals using hydrogenation processes (e.g., ammonia synthesis, [5] methanol production [6] ), as a direct fuel (e.g., in rocket [7] ), in metallurgical industries, [8] semiconductor manufacturing, [9] pharmaceuticals, [8] and any other sectors having concerns related to energy and environment. However, large-scale H 2 production is majorly dependent on steam reforming of fossil fuels (about 96%), [10] and the rest 4% by water electrolysis. [11][12][13][14][15][16][17] Environmentally benign process, water electrolysis needs an exponential growth for the development of a powerful H 2 generator. Noble metals (platinum, palladium, and ruthenium [18] ), especially platinum, are highly The discovery of novel materials for industrial-standard hydrogen production is the present need considering the global energy infrastructure. A novel electrocatalyst, Pt 3 Ge, which is engineered with a desired crystallographic facet (202), accelerates hydrogen production by water electrolysis, and records industrially desired operational stability compared to the commercial catalyst platinum is introduced. Pt 3 Ge-(202) exhibits low overpotential of 21.7 mV (24.6 mV for Pt/C) and 92 mV for 10 and 200 mA cm −2 current density, respectively in 0.5 m H 2 SO 4 . It also exhibits remarkable stability of 15 000 accelerated degradation tests cycles (5000 for Pt/C) and exceptional durability of 500 h (@10 mA cm −2 ) in acidic media. Pt 3 Ge-(202) also displays low overpotential of 96 mV for 10 mA cm −2 current density in the alkaline medium, rationalizing its hydrogen production ability over a wide pH range required commercial operations. Long-term durability (>75 h in alkaline media) with the industrial level current density (>500 mA cm −2 ) has been demonstrated by utilizing the electrochemical flow reactor. The driving force behind this stupendous performance of Pt 3 Ge-(202) has been envisaged by mapping the reaction mechanism, active sites, and charge-transfer kinetics via controlled electrochemical experiments, ex situ X-ray photoelectron spectroscopy, in situ infrared spectroscopy, and in situ X-ray absorption spectroscopy further corroborated by first principles calculations.

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Section: Resultsmentioning

confidence: 99%

Morphology‐Tuned Pt₃Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

et al. 2022

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“…Previous reports show that Ge-based systems exhibit high stability in alkaline medium . The compound Pd 2 Ge has never been tested for OER and is only mentioned in a single report on HER for the reduction counterpart of water splitting . The major concern of the OER catalysts is their mechanical and electronic stability and durability in a harsh alkaline and oxidation environment.…”

Section: Introductionmentioning

confidence: 99%

Distortion-Induced Interfacial Charge Transfer at Single Cobalt Atom Secured on Ordered Intermetallic Surface Enhances Pure Oxygen Production

Mondal,

Riyaz,

Bagchi

et al. 2023

ACS Nano

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In this work, atomic cobalt (Co) incorporation into the Pd2Ge intermetallic lattice facilitates operando generation of a thin layer of CoO over Co-substituted Pd2Ge, with Co in the CoO surface layer functioning as single metal sites. Hence the catalyst has been titled Co1–CoO-Pd2Ge. High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy confirm the existence of CoO, with some of the Co bonded to Ge by substitution of Pd sites in the Pd2Ge lattice. The role of the CoO layer in the oxygen evolution reaction (OER) has been verified by its selective removal using argon sputtering and conducting the OER on the etched catalyst. In situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy demonstrate that CoO gets transformed to CoOOH (Co3+) in operando condition with faster charge transfer through Pd atoms in the core Pd2Ge lattice. In situ Raman spectroscopy depicts the emergence of a CoOOH phase on applying potential and shows that the phase is stable with increasing potential and time without getting converted to CoO2. Density functional theory calculations indicate that the Pd2Ge lattice induces distortion in the CoO phase and generates unpaired spins in a nonmagnetic CoOOH system resulting in an increase in the OER activity and durability. The existence of spin density even after electrocatalysis is verified from electron paramagnetic resonance spectroscopy. We have thus successfully synthesized intermetallic supported CoO during synthesis and rigorously verified the role played by an intermetallic Pd2Ge core in enhancing charge transfer, generating spin density, improving electrochemical durability, and imparting mechanical stability to a thin CoOOH overlayer. Differential electrochemical mass spectrometry has been explored to visualize the instantaneous generation of oxygen gas during the onset of the reaction.

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“…PdSn, Pd 3 Sn 2 , and Pd 2 Sn nanoparticles chemoselectively hydrogenate crotonaldehyde, with PdSn nanoparticles having a high selectivity for the reduction of CO vs CC bonds . Catalytic Pd 3 Sn 2 networks have been used in formic acid electrooxidation, while Pd 2 Ge nanoparticles are active in ethanol oxidation and the hydrogen evolution reaction (HER) . Pd 3 Pb nanoparticles are very active in the electrochemical reduction of oxygen − and of N 2 to NH 3 and in the oxidation of formic acid, , ethanol, , and various amines. , Pd 2 Sn, Pd 2 Ge, and Pd 3 Pb nanoparticles are active in benzylamine oxidation .…”

Section: Introductionmentioning

confidence: 99%

Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations

et al. 2021

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Intermetallic nanoparticles are promising catalysts in hydrogenation and fuel cell technologies. Much is known about the ability of intermetallic nanoparticles to selectively reduce nitro vs alkene, alcohol, or halide functional groups; less is known about their selectivity toward aniline vs azo or azoxy condensation products that result from the reduction of a nitro group alone. Because azo(xy)arenes bear promise as dyes, chemical stabilizers, and building blocks to functional materials but can be difficult to isolate, developing high surface area nanoparticle catalysts that display azo(xy) selectivity is desirable. To address this question, we studied a family of nanocrystalline group 10 metal (Pd, Pt)-and group 14 metal (Ge, Sn, Pb)-containing intermetallicsPd 2 Ge, Pd 2 Sn, Pd 3 Sn 2 , Pd 3 Pb, and PtSnin the catalytic reduction of nitroarenes. In contrast to monometallic Au, Pt, and Pd nanoparticles and ″random″ Pd x Sn 1 − x nanoalloys, which are selective for aniline, nanoparticles of atomically precise intermetallic Pd 2 Ge, Pd 2 Sn, Pd 3 Sn 2 , and PtSn prefer an indirect condensation pathway and have a high selectivity for the azo(xy) products. The only exception is Pd 3 Pb, the most active among the intermetallic nanoparticles studied here, which is instead selective for aniline. Employing a novel application of molecular dynamicsbased on machine learned potentials within a DeePMD frameworkto heterogeneous catalysis, we are able to identify key reaction species on the different types of catalysts employed, furthering our understanding of the unique selectivity of these materials. By demonstrating how intermetallic nanoparticles can be as active yet more selective than other more traditional catalysts, this work provides new physical insights and opens new opportunities in the use of these materials in other important chemical transformations and applications.

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Morphology controlled synthesis of Pd2Ge nanostructures and their shape-dependent catalytic properties for hydrogen evolution reaction

Cited by 9 publications

References 47 publications

Morphology‐Tuned Pt₃Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

Morphology‐Tuned Pt₃Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

Distortion-Induced Interfacial Charge Transfer at Single Cobalt Atom Secured on Ordered Intermetallic Surface Enhances Pure Oxygen Production

Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations

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Morphology controlled synthesis of Pd2Ge nanostructures and their shape-dependent catalytic properties for hydrogen evolution reaction

Cited by 9 publications

References 47 publications

Morphology‐Tuned Pt3Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

Morphology‐Tuned Pt3Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

Distortion-Induced Interfacial Charge Transfer at Single Cobalt Atom Secured on Ordered Intermetallic Surface Enhances Pure Oxygen Production

Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations

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Morphology‐Tuned Pt₃Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range

Morphology‐Tuned Pt₃Ge Accelerates Water Dissociation to Industrial‐Standard Hydrogen Production over a wide pH Range