Atomistic and electronic structure of metal clusters supported on transition metal carbides: implications for catalysis

Mapping Intimacies ◽

10.33774/chemrxiv-2021-v2xzd ◽

2021 ◽

Author(s):

Hector Prats ◽

Michail Stamatakis

Keyword(s):

Catalytic Activity ◽

Transition Metal ◽

Electron Density ◽

High Throughput Screening ◽

Density Functional ◽

Metal Cluster ◽

High Catalytic Activity ◽

Metal Carbides ◽

Oxide Supports ◽

Transition Metal Carbides

Novel research avenues have been explored over the last decade on the use of transition metal carbides (TMCs) as catalytically active supports for metal nanoclusters, which display high catalytic activity despite the poor reactivity (or even inertness) of the bulk metal. It has been postulated that TMCs polarise the electron density of adsorbed metal particles in such a way that their catalytic activity ends up being superior to those dispersed on more traditional metal oxide supports. Herein, we investigate the structural and electronic properties of small clusters of precious metals (Rh, Pd, Pt and Au) and more affordable metals (Co, Ni and Cu) supported on TMCs with 1:1 stoichiometry (TiC, ZrC, HfC, VC, NbC, TaC, MoC and WC) by means of periodic Density Functional Theory calculations. Our high-throughput screening studies indicate that it is possible not only to have strongly bonded and stably dispersed metal nanoparticles on TMC surfaces, but also to manipulate their charge by carefully selecting elements with desired electronegativity for the host TMC and the metal cluster. By doing so, it is possible to tune the amount of charge density on the cluster hollow sites, which can facilitate the bonding of certain molecules. Moreover, we identify Pt, Pd and Rh clusters supported on hexagonal TMC (001) facets as the candidates with the highest potential catalytic activity -as estimated by the significant polarisation of the cluster electron density- and stability -as quantified by the strongly negative values of adsorption energy per atom and formation energy-.

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Atomistic and electronic structure of metal clusters supported on transition metal carbides: implications for catalysis

Journal of Materials Chemistry A ◽

10.1039/d1ta08468b ◽

2022 ◽

Author(s):

Hector Prats ◽

Michail Stamatakis

Keyword(s):

Electronic Structure ◽

Catalytic Activity ◽

Transition Metal ◽

Metal Clusters ◽

High Catalytic Activity ◽

Metal Nanoclusters ◽

Metal Carbides ◽

Transition Metal Carbides ◽

Structure Of Metal ◽

Catalytically Active

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Tuning Transition Metal Carbides Activity by Surface Metal Alloying: Case Study on CO2 Capture and Activation

10.26434/chemrxiv.6377330.v1 ◽

2018 ◽

Author(s):

Marti Lopez ◽

Luke Broderick ◽

John J Carey ◽

Francesc Vines ◽

Michael Nolan ◽

...

Keyword(s):

Transition Metal ◽

Co2 Capture ◽

Density Functional ◽

Deep Understanding ◽

Metal Carbides ◽

Transition Metal Carbides ◽

Adsorption Sites ◽

Surface Metal ◽

A Minor

<div>CO2 is one of the main actors in the greenhouse effect and its removal from the atmosphere is becoming an urgent need. Thus, CO2 capture and storage (CCS) and CO2 capture and usage (CCU) technologies are intensively investigated as technologies to decrease the concentration</div><div>of atmospheric CO2. Both CCS and CCU require appropriate materials to adsorb/release and adsorb/activate CO2, respectively. Recently, it has been theoretically and experimentally shown that transition metal carbides (TMC) are able to capture, store, and activate CO2. To further improve the adsorption capacity of these materials, a deep understanding of the atomic level processes involved is essential. In the present work, we theoretically investigate the possible effects of surface metal doping of these TMCs by taking TiC as a textbook case and Cr, Hf, Mo, Nb, Ta, V, W, and Zr as dopants. Using periodic slab models with large</div><div>supercells and state-of-the-art density functional theory based calculations we show that CO2 adsorption is enhanced by doping with metals down a group but worsened along the d series. Adsorption sites, dispersion and coverage appear to play a minor, secondary constant effect. The dopant-induced adsorption enhancement is highly biased by the charge rearrangement at the surface. In all cases, CO2 activation is found but doping can shift the desorption temperature by up to 135 K.</div>

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Exploring the possibilities of two-dimensional transition metal carbides as anode materials for sodium batteries

Physical Chemistry Chemical Physics ◽

10.1039/c4cp05140h ◽

2015 ◽

Vol 17 (7) ◽

pp. 5000-5005 ◽

Cited By ~ 86

Author(s):

Eunjeong Yang ◽

Hyunjun Ji ◽

Jaehoon Kim ◽

Heejin Kim ◽

Yousung Jung

Keyword(s):

Density Functional Theory ◽

Transition Metal ◽

Electrochemical Properties ◽

Anode Materials ◽

Density Functional ◽

Two Dimensional ◽

Metal Carbides ◽

Functional Theory ◽

Transition Metal Carbides ◽

Sodium Batteries

MXenes are predicted to be a family of promising Na anode materials with desirable electrochemical properties using density functional theory.

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Density functional theory studies of transition metal carbides and nitrides as electrocatalysts

Chemical Society Reviews ◽

10.1039/d1cs00590a ◽

2021 ◽

Author(s):

Dong Tian ◽

Steven R. Denny ◽

Kongzhai Li ◽

Hua Wang ◽

Shyam Kattel ◽

...

Keyword(s):

Density Functional Theory ◽

Transition Metal ◽

Density Functional ◽

Dft Studies ◽

Metal Carbides ◽

Functional Theory ◽

Future Outlook ◽

Transition Metal Carbides

This review summarizes density functional theory (DFT) studies of TMCs and TMNs as electrocatalysts. It provides atomistic details of HER, OER, ORR, N2RR and CO2RR and also presents a future outlook in designing TMCs and TMNs based electrocatalysts.

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Tuning transition metal carbide activity by surface metal alloying: a case study on CO2capture and activation

Physical Chemistry Chemical Physics ◽

10.1039/c8cp03648a ◽

2018 ◽

Vol 20 (34) ◽

pp. 22179-22186 ◽

Cited By ~ 4

Author(s):

Martí López ◽

Luke Broderick ◽

John J. Carey ◽

Francesc Viñes ◽

Michael Nolan ◽

...

Keyword(s):

Transition Metal ◽

Density Functional ◽

State Of The Art ◽

Transition Metal Carbide ◽

Metal Carbide ◽

Metal Carbides ◽

Early Transition Metal ◽

Transition Metal Carbides ◽

Surface Metal

The CO2capture and activation on early transition metal carbides can be fine-tuned by surface doping of similar metals as evidenced by state-of-the-art density functional simulations of the adsorption and desorption rates on suited models.

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First-principles study of rocksalt early transition-metal carbides as potential catalysts for Li–O2 batteries

Physical Chemistry Chemical Physics ◽

10.1039/c8cp06745g ◽

2018 ◽

Vol 20 (48) ◽

pp. 30231-30238 ◽

Cited By ~ 3

Author(s):

Yingying Yang ◽

Yuelin Wang ◽

Man Yao ◽

Xudong Wang ◽

Hao Huang

Keyword(s):

Catalytic Activity ◽

Transition Metal ◽

First Principles ◽

First Principles Calculations ◽

Metal Carbides ◽

Early Transition Metal ◽

Transition Metal Carbides ◽

First Principles Study ◽

Early Transition

A series of early transition-metal carbides (TMCs) in the NaCl structure have been constructed to compare the catalytic activity in Li–O2 batteries by first-principles calculations.

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