Oxidative Cleavage of the β-O-4 Linkage of Lignin by Transition Metals: Catalytic Properties and the Performance of Density Functionals

Wang, Jiaqi; Liu, Lily; Wilson, Angela K.

doi:10.1021/acs.jpca.5b08854

Cited by 25 publications

(22 citation statements)

References 74 publications

(120 reference statements)

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“…The common methods of utilizing lignin under research include hydrothermal processing (carbonification), catalytic wet oxidation, reductive catalytic fractionation, pyrolysis, gasification, dehydroxygenation, and enzymatic degradation. [ 127,128 ] Recent years, extracting natural lignin to achieve almost theoretical yield of monomers was a big breakthrough in lignin valorization, [ 128,129 ] which opened a new window for the biorefinery area. Integrated utilization of lignin to produce high yield phenol, propylene, and printing ink is another fresh breakthrough in the area.…”

Section: Computational Modeling Of Ligninmentioning

confidence: 99%

Understanding Plant Biomass via Computational Modeling

2020

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Plant biomass, especially wood, has been used for structural materials since ancient times. It is also showing great potential for new structural materials and it is the major feedstock for the emerging biorefineries for building a sustainable society. The plant cell wall is a hierarchical matrix of mainly cellulose, hemicellulose, and lignin. Herein, the structure, properties, and reactions of cellulose, lignin, and wood cell walls, studied using density functional theory (DFT) and molecular dynamics (MD), which are the widely used computational modeling approaches, are reviewed. Computational modeling, which has played a crucial role in understanding the structure and properties of plant biomass and its nanomaterials, may serve a leading role on developing new hierarchical materials from biomass in the future.

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Section: Computational Modeling Of Ligninmentioning

confidence: 99%

Understanding Plant Biomass via Computational Modeling

2020

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“…More recently, some kinetic modeling and analysis has been carried out, particularly to model fast pyrolysis [45][46][47][48][49][50] . Both specific 51 and general catalysis of lignin depolymerization has been investigated computationally by studying the effect of transition metal catalysts [52][53][54][55] and ionic liquids [56][57] on lignin degradation. Few studies [58][59] have focused on the more complex chemistry of the other seven linkages in lignin, despite the fact that β-O-4 may comprise as little as 35% of the lignin linkages, depending upon the feedstock 60 .…”

Section: Introductionmentioning

confidence: 99%

Depolymerization Pathways for Branching Lignin Spirodienone Units Revealed with ab Initio Steered Molecular Dynamics

Mar

Kulik

2017

J. Phys. Chem. A

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Lignocellulosic biomass is an abundant, rich source of aromatic compounds, but direct utilization of raw lignin has been hampered by both the high heterogeneity and variability of linking bonds in this biopolymer. Ab initio steered molecular dynamics (AISMD) has emerged both as a fruitful direct computational screening approach to identify products that occur through mechanical depolymerization (i.e., in sonication or ball-milling) and as a sampling approach. By varying the direction of force and sampling over 750 AISMD trajectories, we identify numerous possible pathways through which lignin depolymerization may occur in pyrolysis or through catalytic depolymerization as well. Here, we present eight unique major depolymerization pathways discovered via AISMD for the recently characterized spirodienone lignin branchinglinkage that may comprise around 10% weight of all lignin in some softwoods. We extract representative trajectories from AISMD and carry out reaction pathway analysis to identify energetically favorable pathways for lignin depolymerization. Importantly, we identify dynamical effects that could not be observed through more traditional calculations of bond dissociation energies. Such effects include thermodynamically favorable recovery of aromaticity in the dienone ring that leads to near-barrierless subsequent ether cleavage and hydrogen bonding effects that stabilize newly formed radicals. Some of the most stable spirodienone fragments that reside at most 1 eV above the reactant structure are formed with only 2 eV barriers for C-C bond cleavage, suggesting key targets for catalyst design to drive targeted depolymerization of lignin.2

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“…The setup of a reliable benchmark of similar quality and extension as GMTKN55 for transition-metal complexes is currently not possible in our opinion, but encouraging steps in this direction were published recently. 233,234 We are aware that the ''zoo'' of DFT-based methods is large and continues to grow. While we could not consider every possible DFA in this study, [235][236][237] we are confident that we have provided a valuable starting point for future studies that would also assess those.…”

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confidence: 99%

A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions

Goerigk

Hansen

Bauer

et al. 2017

Phys. Chem. Chem. Phys.

1,542

2,322

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We present the GMTKN55 benchmark database for general main group thermochemistry, kinetics and noncovalent interactions. Compared to its popular predecessor GMTKN30 [Goerigk and Grimme J. Chem. Theory Comput., 2011, 7, 291], it allows assessment across a larger variety of chemical problems-with 13 new benchmark sets being presented for the first time-and it also provides reference values of significantly higher quality for most sets. GMTKN55 comprises 1505 relative energies based on 2462 single-point calculations and it is accessible to the user community via a dedicated website. Herein, we demonstrate the importance of better reference values, and we re-emphasise the need for London-dispersion corrections in density functional theory (DFT) treatments of thermochemical problems, including Minnesota methods. We assessed 217 variations of dispersion-corrected and -uncorrected density functional approximations, and carried out a detailed analysis of 83 of them to identify robust and reliable approaches. Double-hybrid functionals are the most reliable approaches for thermochemistry and noncovalent interactions, and they should be used whenever technically feasible. These are, in particular, DSD-BLYP-D3(BJ), DSD-PBEP86-D3(BJ), and B2GPPLYP-D3(BJ). The best hybrids are ωB97X-V, M052X-D3(0), and ωB97X-D3, but we also recommend PW6B95-D3(BJ) as the best conventional global hybrid. At the meta-generalised-gradient (meta-GGA) level, the SCAN-D3(BJ) method can be recommended. Other meta-GGAs are outperformed by the GGA functionals revPBE-D3(BJ), B97-D3(BJ), and OLYP-D3(BJ). We note that many popular methods, such as B3LYP, are not part of our recommendations. In fact, with our results we hope to inspire a change in the user community's perception of common DFT methods. We also encourage method developers to use GMTKN55 for cross-validation studies of new methodologies.

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Oxidative Cleavage of the β-O-4 Linkage of Lignin by Transition Metals: Catalytic Properties and the Performance of Density Functionals

Cited by 25 publications

References 74 publications

Understanding Plant Biomass via Computational Modeling

Understanding Plant Biomass via Computational Modeling

Depolymerization Pathways for Branching Lignin Spirodienone Units Revealed with ab Initio Steered Molecular Dynamics

A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions

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