Design Principles for Multinary Metal Chalcogenides: Toward Programmable Reactivity in Energy Conversion

Perryman, Joseph T.; Velázquez, Jesús M.

doi:10.1021/acs.chemmater.1c01983

Cited by 17 publications

(12 citation statements)

References 133 publications

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“…We note that these proposed NRR screening criteria differ from the previously suggested NRR scaling relations of N 2 → *NNH vs *NH 2 → NH 3 . The multinary Chevrel phases may provide an ideal platform for designing superior NRR electrocatalysts due to the similarity of their active sites to the nitrogenase cofactors and their tunable compositions that allow a range of chalcogenide stoichiometries and transition-metal intercalants. − Expanding the set of NRR electrocatalysts that break scaling relations via GC-DFT studies may elucidate the importance of narrow bands of surface d -states near −6.5 eV below the Fermi level, concomitant N 2 adsorption and subsurface bond dissociation, and the trigonal pyramidal active site geometry (tetrahedral with *N x H y ).…”

Section: Resultsmentioning

confidence: 92%

How the Bioinspired Fe₂Mo₆S₈ Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

Singstock

Musgrave

2022

J. Am. Chem. Soc.

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The nitrogen reduction reaction (NRR) is a renewable alternative to the energy-and CO 2 -intensive Haber− Bosch NH 3 synthesis process but is severely limited by the low activity and selectivity of studied electrocatalysts. The Chevrel phase Fe 2 Mo 6 S 8 has a surface Fe−S−Mo coordination environment that mimics the nitrogenase FeMo-cofactor and was recently shown to provide state-of-the-art activity and selectivity for NRR. Here, we elucidate the previously unknown NRR mechanism on Fe 2 Mo 6 S 8 via grand-canonical density functional theory (GC-DFT) that realistically models solvated and biased surfaces. Fe sites of Fe 2 Mo 6 S 8 selectively stabilize the key *NNH intermediate via a narrow band of free-atom-like surface d-states that selectively hybridize with p-states of *NNH, which results in Fe sites breaking NRR scaling relationships. These sharp d-states arise from an Fe−S bond dissociation during N 2 adsorption that mimics the mechanism of the nitrogenase FeMo-cofactor. Furthermore, we developed a new GC-DFT-based approach for calculating transition states as a function of bias (GC-NEB) and applied it to produce a microkinetic model for NRR at Fe 2 Mo 6 S 8 that predicts high activity and selectivity, in close agreement with experiments. Our results suggest new design principles that may identify effective NRR electrocatalysts that minimize the barriers for *N 2 protonation and *NH 3 desorption and that may be broadly applied to the rational discovery of stable, multinary electrocatalysts for other reactions where narrow bands of surface d-states can be tuned to selectively stabilize key reaction intermediates and guide selectivity toward a target product. Furthermore, our results highlight the importance of using GC-DFT and GC-NEB to accurately model electrocatalytic reactions.

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Section: Resultsmentioning

confidence: 92%

How the Bioinspired Fe₂Mo₆S₈ Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

Singstock

Musgrave

2022

J. Am. Chem. Soc.

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“…The design of multinary nanocrystals was aimed at improving the catalytic activity and stability of binary transition metal chalcogenides. [138][139][140][141][142] A multinary transition metal compound is composed of at least two different metals. The formation of multinary transition metal chalcogenide introduces some unique properties different from those of binary compounds while retaining inherent properties.…”

Section: Photo-electrochemical (Pec) Water Splittingmentioning

confidence: 99%

Recent advances in solution assisted synthesis of transition metal chalcogenides for photo-electrocatalytic hydrogen evolution

Gautam

Pal

2022

Phys. Chem. Chem. Phys.

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“…Photocatalytic reduction of both CO 2 and H + are thus thermodynamically favorable. To promote the selective reduction of CO 2 may require doping the QDs or interfacing QDs with CO 2 -reduction cocatalysts, potentially including MoS 2 or other transition metal chalcogenides. − Recent reports have highlighted the potential to control products of photocatalytic reduction of CO 2 or H + with the size of QDs. , Products of CO 2 reduction at M x V 2 O 5 /QD and M x M y ′ V 2 O 5 /QD heterostructures may thus depend on the energy of electrons in QDs. A range of II–VI and III–V QDs, readily interfaced with M x V 2 O 5 or M x M y ′ V 2 O 5 surfaces via SILAR or LAA, have bulk E c values within and more negative than relevant CO 2 -reduction potentials (Figure B).…”

Section: Prospects For Photocatalysis Beyond Hydrogen Evolutionmentioning

confidence: 99%

Lone but Not Alone: Precise Positioning of Lone Pairs for the Design of Photocatalytic Architectures

et al. 2022

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With current economic growth and consumption trends projected to bring about a precipitous and rapid rise of the global temperature, the world stands at a crossroads with regards to climate change. The rate at which greenhouse gas emissions from fossil fuels, industry, and land-use is curtailed over the next decade will determine the trajectory of global warming for the rest of the century. It is increasingly apparent that far-reaching decarbonization of the transportation infrastructure will need to be supplemented by extensive carbon capture, storage, and utilization. Taking a leaf from Nature's playbook, photocatalytic architectures that can utilize water or CO 2 in conjunction with energy harvested from sunlight and store it in the form of energy-dense chemical bonds represent an attractive proposition. Harnessing solar irradiance, through solar energy conversion involving photovoltaics, as well as the photocatalytic generation of solar fuels, and the photocatalytic reduction of CO 2 have emerged as urgent imperatives for the energy transition. Functional photocatalysts must be capable of efficiently absorbing sunlight, effectively separating electronhole pairs, and ensuring they are delivered at appropriate potentials to catalytic sites to mediate redox reactions. Such photocatalytic architectures must further direct redox events down specific pathways to yield desired products, and ensure the transport of reactants between catalytic sites; all with high efficiency and minimal degradation. In this Perspective, we describe a palette of heterostructures designed to promote robust and efficient direct solar-driven water splitting and CO 2 reduction. The heterostructures comprise M x V 2 O 5 or M x M y ′V 2 O 5 , where M is a p-block cation, M′ is an s-, p-, or d-block cation, and V 2 O 5 represents one of multiple polymorphs of this composition interfaced with semiconductor quantum dots (QDs, binary or ternary II−VI or III−V QDs). The stereochemically active 5/6s 2 electron lone pairs of p-block cations in M x V 2 O 5 give rise to filled midgap electronic states that reside above the O 2p-derived valence band. Within heterostructures, the photoexcitation of QDs results in the transfer of holes to the midgap states of M x V 2 O 5 or M x M y ′V 2 O 5 on subpicosecond time scales. Ultrafast charge separation minimizes the photoanodic corrosion of QDs, which has historically been a major impediment to their use in photocatalysis, and enables charge transport and the subsequent redox reactions underpinning photocatalysis to compete with electron−hole recombination. The energy positioning and dispersion of lone pair states is tunable through multiple chemical and compositional levers accessible across the palette of M x V 2 O 5 or M x M y ′V 2 O 5 compounds: choice of lone-pair cation M and its stoichiometry x, atomic connectivity of V 2 O 5 polymorphs, cointercalation of M′ cations in "quaternary" vanadium oxide bronzes, anionic substitution, and alternative lone pair vanadate frameworks with altogether different c...

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Design Principles for Multinary Metal Chalcogenides: Toward Programmable Reactivity in Energy Conversion

Cited by 17 publications

References 133 publications

How the Bioinspired Fe₂Mo₆S₈ Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

How the Bioinspired Fe₂Mo₆S₈ Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

Recent advances in solution assisted synthesis of transition metal chalcogenides for photo-electrocatalytic hydrogen evolution

Lone but Not Alone: Precise Positioning of Lone Pairs for the Design of Photocatalytic Architectures

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Design Principles for Multinary Metal Chalcogenides: Toward Programmable Reactivity in Energy Conversion

Cited by 17 publications

References 133 publications

How the Bioinspired Fe2Mo6S8 Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

How the Bioinspired Fe2Mo6S8 Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

Recent advances in solution assisted synthesis of transition metal chalcogenides for photo-electrocatalytic hydrogen evolution

Lone but Not Alone: Precise Positioning of Lone Pairs for the Design of Photocatalytic Architectures

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How the Bioinspired Fe₂Mo₆S₈ Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

How the Bioinspired Fe₂Mo₆S₈ Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations