rNets: A standalone package to visualize reaction networks. DOI Creative Commons
Sergio Pablo‐García, Raúl Pérez‐Soto, Albert Sabadell‐Rendón

et al.

Published: April 3, 2024

In the study of chemical reactions, visualizing reaction networks is pivotal for identifying crucial compounds and reactions. Traditional methods, such as network schematics path linear plots, often struggle to effectively represent complex due their size intricate connectivity. Alternatives capable leading with complexity include graph but they are not user-friendly, lacking simplicity modularity, which hinders integration widely-used research software. This work introduces rNets an innovative tool designed efficient visualization a user-friendly interface, seamless existing software packages. The effectiveness demonstrated through its application in analyzing three catalytic showcasing potential significantly enhance both homogeneous heterogeneous catalysis fields. only simplifies process also opens new avenues exploring diverse contexts.

Language: Английский

Thinking about the Box: Exploring the Electronic Structure of a Cuboidal-Shaped Mo84 Anionic Nanocapsule DOI
Diego Garay‐Ruiz, Jordi Buils, Nuno A. G. Bandeira

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: 64(6), P. 2716 - 2722

Published: Jan. 30, 2025

The cubic-shaped polyoxothiomolybdate [Mo84O188S48(AcO)24]40- first reported by Cadot and collaborators has been characterized DFT methods for the time, elucidating its electronic structure means of analysis density states as well frontier molecular orbitals. Moreover, electron this complex oxo-cluster studied through QTAIM analysis, focusing on characteristic Mo(V)-Mo(V) bonding pattern appearing at corner subunits nanocapsule.

Language: Английский

Citations

1
Commentary on the role of polyoxometalates in nature cybernetic loop DOI Creative Commons
Kirill Yu. Monakhov

Natural Sciences, Journal Year: 2024, Volume and Issue: 4(2-3)

Published: Jan. 4, 2024

Abstract The interplay between extraterrestrial, atmospheric, aqueous, interfacial, and hydrothermal processes is crucial for Earth's prebiotic chemistry. Volcanic terrains contain polyoxometalates (POMs). Some polyoxocuprates were identified as building blocks of fumarole minerals produced from high‐temperature gases. existence polyoxovanadate anions in acidified reducing volcanic aquifers cannot be excluded. At present, it can only speculated whether life arose around natural POM deposits and/or their aqueous phase chemistry through acid‐base redox reactions. This Commentary spans different fields sciences nature cybernetic loop to provide impetus explore gas‐phase chemical reactions multiply charged ions, catalysis by POM‐containing mineral phases, the behavior POMs under plasma‐initiated ultraviolet photolysis, interactions with microorganisms, bioorthogonal POMs, engineering POM‐based bionic functions inspired living organisms.

Language: Английский

Citations

4
Protonolysis and Condensation Reactions of Alkoxido-Substituted Lindqvist {MW5} and Keggin {MPW11} Polyoxometalates: Comparative Experimental and Modeling Studies DOI Creative Commons

Daniel Lebbie,

Thompson Izuagie, Magda Pascual‐Borrás

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

An understanding of proton transfer and migration at the surfaces solid metal oxides related molecular polyoxometalates (POMs) alkoxides is crucial for development reactivity involving protonation or absorption/binding water. In this work, hydrolysis alkoxido Ti- Sn-substituted Lindqvist [(MeO)MW5O18]3– (M = Ti, 1; M Sn, 2) Keggin [(MeO)MPW11O39]4– 3; 4) type to hydroxido derivatives subsequent condensation μ-oxido species has been investigated in detail provide insight into reactions these oxide systems. Solution NMR studies revealed dependence not only on nature heteroatom (Ti Sn) but also lacunary (W5 PW11) POM solvent (MeCN DMSO). Tin-substituted anions 2 4 were much more susceptible protonolysis than Ti analogues 1 3 while {MW5} generally faster those {MPW11} anions. Subsequent resulting [(HO)MW5O18]3– 5; 6) [(HO)MPW11O39]4– 7; 8) was significantly facile 5 7 and, all cases, inhibited DMSO. Quantitative comparisons equilibria reaction rates provided by analysis kinetic experiments, DFT calculations analogous {NbW5} comparative energetics profiles that are consistent with experimental observations. These results add fundamental alkoxide hydrolysis/condensation surfaces.

Language: Английский

Citations

0
Nucleation Roadmap of Reduced Polyoxovanadate-Alkoxide Clusters DOI Creative Commons
Simon Duggan, S. M. Gulam Rabbani, Pere Miró

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

Polyoxovanadate-alkoxides are a growing family of earth-abundant first-row transition metal polynuclear species highly promising for their tunable redox properties. The speciation and nucleation chemical space these is divided into two groups: 1) fully oxidized V(V) monomeric precursors that aggregate Lindqvist-type clusters 2) reduced V(IV) forming cyclic structures. polyoxovanadate-alkoxides with varying alkyl chain lengths, the impact presence templating anions, subsequent evolution to congener were studied by using density functional theory. oxygen-vacant cluster structures was found be endergonic, in agreement previous experimental work. Moreover, reactivity traces water alcohol solvents confirmed main thermodynamic driving force toward formation mixed-valent polyoxovanadate species.

Language: Английский

Citations

0
Microkinetic Assessment of Ligand-Exchanging Catalytic Cycles DOI Creative Commons

Orkhan Abdullayev,

Diego Garay‐Ruiz,

Berta Bori-Bru

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4739 - 4745

Published: March 6, 2025

Computational chemistry has become a fundamental part of the understanding and optimization catalytic processes. Among these, characterization homogeneous organometallic catalysts, combining an active transition metal atom set ligands, is one main fields application these kinds studies. More recently, microkinetic studies have been employed to bridge gap between experimental measurements such as conversion or selectivity Gibbs free energies gathered by computations. In this work, we developed automated framework (MicroKatc) for analysis, tackle yet understudied effect ligand exchange processes that modify nature scaffold in situ. We report rhodium-catalyzed hydroformylation ethylene, confirming acceleration reaction trimethylphosphine (PMe3) displaces carbonyl ligands catalyst means simulations at variable phosphine concentrations, well determination degree rate control (DRC) apparent activation throughout process.

Language: Английский

Citations

0
Revealing the Electrocatalytic Self-Assembly Route from Building Blocks into Giant Mo-Blue Clusters DOI
Ke Li, Shu Zhang,

Kai-Ling Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown

Published: Nov. 3, 2023

The assembly of single-core molybdate into hundreds cores giant molybdenum blue (Mo-blue) clusters has remained a long-standing unresolved scientific puzzle. To reveal this fascinating self-assembly behavior, we demonstrate an aqueous flowing in-operando Raman characterization system to capture the building blocks' evolution from "black box" reaction process. We successfully visualized sequential transformation Na2MoO4 Mo7O246– ({Mo7}), high nuclear Mo36O1128– ({Mo36}) cluster, and finally polymerization product [H6K2Mo3O12(SO4)]n ({Mo3(SO4)}n) during H2SO4 acidification. Notably, facile conversion {Mo3(SO4)}n back {Mo36} cluster by simple dilution is also discovered. Furthermore, identified as exclusive precursors responsible for driving electrochemical {Mo154} {Mo102}, respectively. study unravels pivotal intermediate, pentagonal reduced state fragment [H18MoVI4MoVO24]−, originating {Mo36}, which catalyzes autocatalytic with electron proton injection processes. Concurrently, serves indispensable precursor {Mo102} formation, generating sulfation pentagon blocks [H2Na2O2(H4MoVMoVI4O16SO4)4]4– that facilitate consecutive sphere clusters. As result, complete elucidation pathway Mo-blue derived was obtained, H+/e– redox couple revealed play critical role in catalyzing deassembly precursor, leading formation thermodynamically stable intermediates essential further

Language: Английский

Citations

8
POMSimulator: An open‐source tool for predicting the aqueous speciation and self–assembly mechanisms of polyoxometalates DOI Creative Commons
Enric Petrus, Jordi Buils, Diego Garay‐Ruiz

et al.

Journal of Computational Chemistry, Journal Year: 2024, Volume and Issue: 45(26), P. 2242 - 2250

Published: June 3, 2024

Abstract Elucidating the speciation (in terms of concentration versus pH) and understanding formation mechanisms polyoxometalates remains a significant challenge, both in experimental computational domains. POMSimulator is new methodology that tackles this problem from purely perspective. The uses results quantum mechanics based methods to automatically set up chemical reaction network, build models. As result, it becomes possible predict phase diagrams, as well derive insights into large molecular clusters. In work we present main features first open‐source version software. Since report [Chem. Sci. 2020, 11, 8448‐8456], has undergone several improvements keep with growing challenges were tackled. After four years research, recognize source code sufficiently stable share polished user‐friendly version. Python code, manual, examples, install instructions can be found at https://github.com/petrusen/pomsimulator .

Language: Английский

Citations

3
Emerging polyoxometalate clusters-based redox flow batteries: Performance metrics, application prospects, and development strategies DOI

Mingjun Han,

Wei Sun, Wenjihao Hu

et al.

Energy storage materials, Journal Year: 2024, Volume and Issue: 71, P. 103576 - 103576

Published: June 17, 2024

Language: Английский

Citations

2
rNets: a standalone package to visualize reaction networks DOI Creative Commons
Sergio Pablo‐García, Raúl Pérez‐Soto, Albert Sabadell‐Rendón

et al.

Digital Discovery, Journal Year: 2024, Volume and Issue: 3(8), P. 1564 - 1576

Published: Jan. 1, 2024

In the study of chemical processes, visualizing reaction networks is pivotal for identifying crucial compounds and transformations.

Language: Английский

Citations

2
Computational insights into aqueous speciation of metal-oxide nanoclusters: an in-depth study of the Keggin phosphomolybdate DOI Creative Commons
Jordi Buils, Diego Garay‐Ruiz, Mireia Segado

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(35), P. 14218 - 14227

Published: Jan. 1, 2024

Herein, we present a new computational methodology that unlocks the prediction of complex multi-species multi-equilibria processes involved in formation metal-oxo nanoclusters. Relying on our recently introduced method named POMSimulator, extended its capabilities and challenged accuracy with well-known phosphomolybdate [PMo12O40]3- Keggin anion system. We show how use statistical techniques enabled processing vast number speciation models their associated systems non-linear equations efficiently scalable manner. Subsequently, this approach is applied to generate statistically averaged diagrams error bars. Then, unveil previously unreported phase diagram under varying [Mo]/[P] ratios vs. pH. Our findings align well experimental data, indicating prevalence {PMo12} as primary species at low pH, but lacunary {PMo11}and Strandberg {P2Mo5} anions also emerge major other concentration ratios. Finally, from 7 × 104 inferred plausible reaction network across diverse nuclearities within system, which underlines role trimers key intermediate building blocks.

Language: Английский

Citations

0