A polymeric hydrogel electrocatalyst for direct water oxidation

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Фев. 13, 2023

Metal-free electrocatalysts represent a main branch of active materials for oxygen evolution reaction (OER), but they excessively rely on functionalized conjugated carbon materials, which substantially restricts the screening potential efficient carbonaceous electrocatalysts. Herein, we demonstrate that mesostructured polyacrylate hydrogel can afford an unexpected and exceptional OER activity - par with benchmark IrO2 catalyst in alkaline electrolyte, together high durability good adaptability various pH environments. Combined theoretical electrokinetic studies reveal positively charged atoms within carboxylate units are intrinsically toward OER, spectroscopic operando characterizations also identify fingerprint superoxide intermediate generated polymeric backbone. This work expands scope metal-free by providing new class huge extension potentials.

Язык: Английский

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Rational In Silico Design of Molecularly Imprinted Polymers: Current Challenges and Future Potential

International Journal of Molecular Sciences, Год журнала: 2023, Номер 24(7), С. 6785 - 6785

Опубликована: Апрель 5, 2023

The rational design of molecularly imprinted polymers has evolved along with state-of-the-art experimental imprinting strategies taking advantage sophisticated computational tools. In silico methods enable the screening and simulation innovative polymerization components conditions superseding conventional formulations. combined use quantum mechanics, molecular dynamics allows for macromolecular modelling to study systematic translation from pre- post-polymerization stage. However, predictive high-performance computing advance MIP development are neither fully explored nor practiced comprehensively on a routine basis date. this review, we focus different steps process discuss appropriate that may assist in optimizing associated strategies. We potential, challenges, limitations approaches including ML/AI present perspectives guide next-generation accelerating discovery templated materials.

Язык: Английский

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Hybrid Cluster-Continuum Method for Single-Ion Solvation Free Energy in Acetonitrile Solvent

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(31), С. 6440 - 6449

Опубликована: Июль 25, 2024

A new hybrid discrete-continuum approach named the cluster-continuum static approximation (CCSA) has been proposed for acetonitrile solvent. The continuum part uses conductor-like polarizable model electrostatic and a surface area-dependent term nonelectrostatic solvation. CCSA includes only one explicit solvent molecule damping function, which makes method reduce to pure solvation in case of weaker potential mean force solute-solvent interaction. performance was tested 22 anions cations, including challenge species that cannot be adequately described by comparison done with widely used density (SMD) model. For anions, reduces same as SMD model, standard deviation signed error (SD-MSE) 2.7 kcal mol

Язык: Английский

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Conformational energies of biomolecules in solution: Extending the MPCONF196 benchmark with explicit water molecules

Journal of Computational Chemistry, Год журнала: 2023, Номер 45(7), С. 419 - 429

Опубликована: Ноя. 19, 2023

Abstract A prerequisite for the computational prediction of molecular properties like conformational energies biomolecules is a reliable, robust, and computationally affordable method usually selected according to its performance relevant benchmark sets. However, most these sets comprise molecules in gas phase do not cover interactions with solvent, even though typically occur aqueous solution. To address this issue, we introduce explicit water solvated version gas‐phase set containing 196 conformers 13 peptides other macrocycles, namely MPCONF196 [J. Řezáč et al., JCTC 2018 , 14 1254–1266], provide very accurate PNO‐LCCSD(T)‐F12b/AVQZ' reference values. The novel solvMPCONF196 features two additional challenges beyond description phase: conformer–water water–water interactions. overall best performing double hybrid revDSDPBEP86‐D4/def2‐QZVPP yielding almost coupled cluster quality. Furthermore, some (meta‐)GGAs functionals B97M‐V B97M‐D large basis reproduce an MAD below 1 kcal mol . If more efficient methods are required, composite DFT‐method rSCAN‐3c (MAD 1.2 mol) good alternative, when polypeptides or macrocycles than 500–1000 atoms focus, semi‐empirical GFN2‐xTB MMFF94 force field (for systems) recommended.

Язык: Английский

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Revealing the Hidden Complexity and Reactivity of Palladacyclic Precatalysts: The P(o-tolyl)₃ Ligand Enables a Cocktail of Active Species Utilizing the Pd(II)/Pd(IV) and Pd(0)/Pd(II) Pathways for Efficient Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 12769 - 12782

Опубликована: Авг. 9, 2024

The ligand, P(o-tolyl)3, is ubiquitous in applied synthetic chemistry and catalysis, particularly Pd-catalyzed processes, which typically include Pd(OAc)2 (most commonly used as Pd3(OAc)6) a precatalyst. Herrmann–Beller palladacycle [Pd(C^P)(μ2-OAc)]2 (where C^P = monocyclopalladated P(o-tolyl)3) easily formed from reaction of with P(o-tolyl)3. mechanisms by this precatalyst system operates are inherently complex, studies previously implicating Pd nanoparticles (PdNPs) reservoirs for active Pd(0) species arylative cross-coupling reactions. In study, we reveal the fascinating, nontrivial behavior palladacyclic group. First, presence hydroxide base, readily converted into an activated form, [Pd(C^P)(μ2-OH)]2, serves conduit activation to catalytically relevant species. Second, palladacyclization imparts unique stability catalytic under conditions, bringing play Pd(II)/Pd(IV) mechanism. For benchmark Suzuki–Miyaura (SMCC) reaction, there shift mononuclear pathway PdNP-controlled during reaction. [Pd(C^P)(μ2-OH)]2 has been studied using arylphosphine-stabilized boronic acid low-temperature NMR spectroscopic analysis, sheds light on preactivation step, water and/or being critical formation Pd(II) situ monitoring demonstrated that sensitivity structure arylboron pinacol. This work, taken together, highlights mechanistic complexity accompanying use systems. It builds recent findings involving related Pd(OAc)2/PPh3 systems form higher order Pdn clusters PdNPs conditions. Thus, generally, one needs be cautious assumption Pd(OAc)2/tertiary phosphine mixtures cleanly deliver "Pd(0)Ln" any assessment individual ligands may need case-by-case basis.

Язык: Английский

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Protonated Porphyrins: Bifunctional Catalysts for the Metal‐Free Synthesis of N‐Alkyl‐Oxazolidinones

Chemistry - A European Journal, Год журнала: 2022, Номер 29(1)

Опубликована: Окт. 4, 2022

The protonation of commercially available porphyrin ligands yields a class bifunctional catalysts able to promote the synthesis N-alkyl oxazolidinones by CO

Язык: Английский

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Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(33)

Опубликована: Май 13, 2023

Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO

Язык: Английский

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Elucidating reaction mechanisms in the oxidative depolymerization of sodium lignosulfonate for enhancing vanillin production: A Density Functional Theory study

Journal of Analytical and Applied Pyrolysis, Год журнала: 2024, Номер 179, С. 106499 - 106499

Опубликована: Апрель 10, 2024

Язык: Английский

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Remote Functionalization by Pd-Catalyzed Isomerization of Alkynyl Alcohols

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(27), С. 18606 - 18615

Опубликована: Июнь 28, 2024

In recent years, progress has been made in the development of catalytic methods that allow remote functionalizations based on alkene isomerization. contrast, protocols alkyne isomerization are comparatively rare. Herein, we report a general Pd-catalyzed long-range alkynyl alcohols. Starting from aryl-, heteroaryl-, or alkyl-substituted precursors, optimized system provides access preferentially to thermodynamically more stable α,β-unsaturated aldehydes and is compatible with potentially sensitive functional groups. We showed migration both π-components carbon–carbon triple bond can be sustained over several methylene units. Computational investigations served shed light key elementary steps responsible for reactivity selectivity. These include an unorthodox phosphine-assisted deprotonation rather than conventional β-hydride elimination final tautomerization event.

Язык: Английский

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PyDFT-QMMM: A modular, extensible software framework for DFT-based QM/MM molecular dynamics

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(3)

Опубликована: Июль 15, 2024

PyDFT-QMMM is a Python-based package for performing hybrid quantum mechanics/molecular mechanics (QM/MM) simulations at the density functional level of theory. The program designed to treat short-range and long-range interactions through user-specified combinations electrostatic mechanical embedding procedures within periodic simulation domains, providing necessary interfaces external chemistry molecular dynamics software. To enable direct electrostatics in systems, we have derived implemented force terms our previously described QM/MM/PME approach [Pederson McDaniel, J. Chem. Phys. 156, 174105 (2022)]. Communication with software packages Psi4 OpenMM facilitated Python application programming (APIs). core library contains basic utilities running QM/MM simulations, plug-in entry-points are provided users implement custom energy/force calculation integration routines, an extensible architecture. user interacts primarily its API, allowing complex workflow development scripting, example, interfacing PLUMED free energy simulations. We provide benchmarks forces conservation alternative approaches. further demonstrate simple example use case water solute solvent system, which radial distribution functions computed from 100 ps simulations; this highlight how solvation structure sensitive different basis-set choices due under- or over-polarization QM molecule’s electron density.

Язык: Английский

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