Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO<sub>2</sub> reduction reaction

Pankhurst, James R.; Iyengar, Pranit; Loiudice, Anna; Mensi, Mounir; Buonsanti, Raffaella

doi:10.1039/d0sc03061a

Cited by 56 publications

(64 citation statements)

References 37 publications

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“…97 In contrast, a recent paper from Buonsanti et al showed complete removal of native phosphate and trialkylamine ligands from the surface of Cu 0 nanospheres. 98…”

Section: Resultsmentioning

confidence: 99%

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Murphy

Rice

Monahan

et al. 2021

Preprint

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Covalent functionalization of Ni2P nanocrystals was demonstrated using aryl-diazonium salts. Spontaneous adsorption of aryl functional groups was observed, with surface coverages ranging from 20-96% depending on the native reactivity of the salt as determined by the aryl substitution pattern. Increased coverage was possible for low reactivity species using a sacrificial reductant. Functionalization was confirmed using thermogravimetric analysis, FTIR and X-ray photoelectron spectroscopy. The structure and energetics of this nanocrystal electrocatalyst system, as a function of ligand coverage, was explored with density functional theory calculations. The Hammett parameter of the surface functional group was found to linearly correlate with the change in Ni and P core-electron binding energies and the nanocrystal's work-function. The electrocatalytic activity and stability of the functionalized nanocrystals for hydrogen evolution were also improved when compared to the unfunctionalized material, but a simple trend based on electrostatics was not evident.

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“…97 In contrast, a recent paper from Buonsanti et al showed complete removal of native phosphate and trialkylamine ligands from the surface of Cu 0 nanospheres. 98…”

Section: Resultsmentioning

confidence: 99%

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Murphy

Rice

Monahan

et al. 2021

Preprint

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“…The research used Cu nanoparticle as benchmark catalysts to investigate the effects of capped different organic ligands (Fig. 9 f) (i.e., oleylamine (OLAM), oleic acid (OLAC), dodecanethiol (DDT), trioctylphosphine (TOP), trioctylphosphine oxide (TOPO), and tetradecylphosphonic acid (TDPA)) on the CO 2 RR activity [ 204 ]. The selection of ligands is based on the following three reasons, i.e., wide range of applications, varied binding strength derived from different functional groups, and a typical research case for studying the correlations between catalytic activity and ligand surface coverage.…”

Section: Interface Engineering For Co 2 Rrmentioning

confidence: 99%

“…h Changes in the charge-transfer resistance (R CT ) over time for CuNCs capped by different ligands. Reprinted with permission from Ref [204].…”

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confidence: 99%

Recent Advances in Interface Engineering for Electrocatalytic CO2 Reduction Reaction

Abbas

Wang

et al. 2021

Nano-Micro Lett.

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Electrocatalytic CO2 reduction reaction (CO2RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels, which can dramatically reduce CO2 emission and contribute to carbon-neutral cycle. Efficient electrocatalytic reduction of chemically inert CO2 is challenging from thermodynamic and kinetic points of view. Therefore, low-cost, highly efficient, and readily available electrocatalysts have been the focus for promoting the conversion of CO2. Very recently, interface engineering has been considered as a highly effective strategy to modulate the electrocatalytic performance through electronic and/or structural modulation, regulations of electron/proton/mass/intermediates, and the control of local reactant concentration, thereby achieving desirable reaction pathway, inhibiting competing hydrogen generation, breaking binding-energy scaling relations of intermediates, and promoting CO2 mass transfer. In this review, we aim to provide a comprehensive overview of current developments in interface engineering for CO2RR from both a theoretical and experimental standpoint, involving interfaces between metal and metal, metal and metal oxide, metal and nonmetal, metal oxide and metal oxide, organic molecules and inorganic materials, electrode and electrolyte, molecular catalysts and electrode, etc. Finally, the opportunities and challenges of interface engineering for CO2RR are proposed.

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“…In some reactions, the real active center comprises single metal atoms with functional ligands, as well as well‐defined surfaces [211–212] . The ligand may control the oxidation state, geometry, and d n electron configuration of the metal center, [212] contributing significantly to the activity, selectivity, and stability of catalysts [213–219] . Depending on the ligands and supports attached to the center metal, the performance of prepared SACs may vary substantially [220–221] .…”

Section: Understanding Of Active Centermentioning

confidence: 99%

“…[211][212] The ligand may control the oxidation state, geometry, and d n electron configuration of the metal center, [212] contributing significantly to the activity, selectivity, and stability of catalysts. [213][214][215][216][217][218][219] Depending on the ligands and supports attached to the center metal, the performance of prepared SACs may vary substantially. [220][221] Taking Pt SACs as an example, powdered MgO, Al 2 O 3 , and CeO 2 were used as supports to anchor a Pt single atom with a ligand 3,6-di-2pyridyl-1,2,4,5tetrazine (DPTZ).…”

Section: Single Atom With Ligands and Supportsmentioning

confidence: 99%

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

Wang

Liu

2020

ChemCatChem

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Single‐atom catalysts (SACs) have been rising recently as a new frontier in the catalysis field. Due to maximum atom utilization efficiency and tunable electronic structures, SACs exhibit highly distinctive catalytic performance from bulk counterparts. SACs with high metal loading will facilitate practical applications. To that end, this Review focuses on recent strategies to maximize metal loading. An appropriate substrate, mainly heteroatom‐doped carbon materials, is the key to avoiding aggregation or sintering during synthetic procedures. The coordination site construction and spatial confinement strategies are adopted to prepare SACs with high metal loading. Advanced characterization techniques with atomic resolution are indispensable for identification of the exact structure of SACs. This is true, especially for the applications and challenges in developing in situ/operando characterization techniques at the atomic level, which are discussed in this Review. Moreover, it is fundamentally necessary to investigate the active center structure, which facilitates any design of efficient SACs that can maximize single‐atom catalytic activity. Furthermore, this Review highlights challenges and prospects for development of SACs.

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Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO₂ reduction reaction

Abstract: Colloidally synthesised nanocrystals (NCs) are increasingly utilised as catalysts to drive both thermal and electrocatalytic reactions. Their well-defined size and shape, controlled by organic ligands, are ideal to identify the...

Cited by 56 publications

References 37 publications

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Recent Advances in Interface Engineering for Electrocatalytic CO2 Reduction Reaction

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

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Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO2 reduction reaction

Abstract: Colloidally synthesised nanocrystals (NCs) are increasingly utilised as catalysts to drive both thermal and electrocatalytic reactions. Their well-defined size and shape, controlled by organic ligands, are ideal to identify the...

Cited by 56 publications

References 37 publications

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Recent Advances in Interface Engineering for Electrocatalytic CO2 Reduction Reaction

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

Contact Info

Product

Resources

About

Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO₂ reduction reaction