Diels–Alder Conversion of Acrylic Acid and 2,5‐Dimethylfuran to <i>para</i>‐Xylene Over Heterogeneous Bi‐BTC Metal‐Organic Framework Catalysts Under Mild Conditions

Wang, Wen‐Lun; Chen, Season S.; Li, Shih‐Cheng; Chen, Celine H.; Shishido, Tetsuya; Tsang, Daniel C.W.; Yamauchi, Yusuke; Li, Yi‐Pei; Wu, Kevin C.‐W.

doi:10.1002/ange.202013061

Cited by 9 publications

(3 citation statements)

References 45 publications

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“…The compatibility of the P 2 parameter set with ωB97X-V is particularly noteworthy, given its relevance for studying adsorption and reactions in MOFs incorporating period 6 elements ( e.g. , Hf, 97,98 Pb, 99,100 and Bi 8 ), which are beyond the empirical dispersion correction of ωB97X-D. However, it is important to note the higher computational demand of ωB97X-V compared to ωB97X-D, a factor that will be discussed in the next subsection.…”

Section: Qm/mm Validationmentioning

confidence: 99%

“…5–7 In previous studies, small cluster models encompassing only the metal nodes have been used to investigate the role of the metal center in MOFs. 8–11 However, these small cluster models are often inadequate to model reactions in MOFs accurately because the catalytic behavior is determined not only by the metal center but also by the framework structure, which contributes to the confinement effect on product selectivity. 5 To address this issue, periodic quantum chemical calculations have been applied to describe the extended structure of MOFs.…”

Section: Introductionmentioning

confidence: 99%

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Tailoring parameters for QM/MM simulations: accurate modeling of adsorption and catalysis in zirconium-based metal–organic frameworks

Kao,

Wang,

Yeh

et al. 2024

Phys. Chem. Chem. Phys.

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Section: Qm/mm Validationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tailoring parameters for QM/MM simulations: accurate modeling of adsorption and catalysis in zirconium-based metal–organic frameworks

Kao,

Wang,

Yeh

et al. 2024

Phys. Chem. Chem. Phys.

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“…In recent years, the accuracy and speed of electronic structure calculations via density functional theory (DFT) has been greatly improved, which enables the determination of detailed mechanisms of complex reaction systems, such as solution-phase chemistries or catalytic reactions occurring in porous materials. − However, correctly calculating thermochemistry and rate of reactions remains challenging because the accuracy of calculating these properties strongly depends on the representation of the potential energy surface (PES) and how the energy levels are computed. The standard computational approach treats every vibrational mode as a harmonic oscillator (HO) so that all frequencies and energy levels can be derived from a normal-mode analysis.…”

Section: Introductionmentioning

confidence: 99%

Comparative Analysis of Uncoupled Mode Approximations for Molecular Thermochemistry and Kinetics

Lin

2022

J. Chem. Theory Comput.

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The accurate prediction of thermochemistry and kinetic parameters is an important task for reaction modeling. Unfortunately, the commonly used harmonic oscillator model is often not accurate enough due to the absence of anharmonic effects. In this work, we improve the representation of an anharmonic potential energy surface (PES) using uncoupled mode (UM) approximations, which model the full-dimensional PES as a sum of one-dimensional potentials of each mode. We systematically analyze different PES sampling schemes and coordinate systems for constructing the one-dimensional potentials, and benchmark the performance of UM methods on data sets of molecular thermochemistry and kinetic properties. The results show that the accuracy of the UM approach strongly depends on how the one-dimensional potentials are defined. If one-dimensional potentials are constructed by sampling along normal mode directions (UM-N) or along the directions that minimize intermode coupling (E- and E′-optimized), the accuracies of the predicted properties are not significantly improved compared to the harmonic oscillator model. However, significant improvements can be achieved by sampling the torsional modes separately from the vibrational modes (UM-T and UM-VT). In this work, three types of coordinate systems are examined, including redundant internal coordinates (RIC), hybrid internal coordinates (HIC), and translation-rotation-internal coordinates (TRIC). The HIC and TRIC coordinate systems can outperform RIC since transition state species may contain large-amplitude interfragmentary motions that regular internal coordinates can not describe adequately. Among all the methods we examined, the activation energies and pre-exponential factors calculated using UM-VT with either TRIC or HIC best agree with the reference values. Since UM-VT requires only a number of additional single point energy calculations for each independent mode, the scaling of computational costs of UM-VT is the same as that of the standard harmonic oscillator model, making UM-VT an appealing way of calculating the thermochemistry and kinetic properties for large-size systems.

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The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

et al. 2022

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Biomass‐derived furanic platform molecules have emerged as promising building blocks for renewable chemicals and functional materials. To this aim, the Diels–Alder (DA) cycloaddition stands out as a versatile strategy to convert these renewable resources in highly atom‐efficient ways. Despite nearly a century worth of examples of furan DA chemistry, clear structure–reactivity–stability relationships are still to be established. Detailed understanding of the intricate interplay between kinetics and thermodynamics in these very particular [4+2] cycloadditions is essential to push further development and truly expand the scope beyond the ubiquitous addend combinations of electron‐rich furans and electron‐deficient olefins. Herein, we provide pertinent examples of DA chemistry, taken from various fields, to highlight trends, establish correlations and answer open questions in the field with the aim to support future efforts in the sustainable chemicals and materials production.

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Diels–Alder Conversion of Acrylic Acid and 2,5‐Dimethylfuran to para‐Xylene Over Heterogeneous Bi‐BTC Metal‐Organic Framework Catalysts Under Mild Conditions

Cited by 9 publications

References 45 publications

Tailoring parameters for QM/MM simulations: accurate modeling of adsorption and catalysis in zirconium-based metal–organic frameworks

Tailoring parameters for QM/MM simulations: accurate modeling of adsorption and catalysis in zirconium-based metal–organic frameworks

Comparative Analysis of Uncoupled Mode Approximations for Molecular Thermochemistry and Kinetics

The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

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