Water-catalyzed conversion of glucose to small molecules during hydrothermal carbonization: a density functional theory study

Guo, Shuai; Xiao, Weinan; Zhao, Deng; Liu, Zhaoyuan; Liu, Lidong; Xu, Dandan; Li, Xingcan; Li, Guangyu

doi:10.1039/d2se01733d

Cited by 6 publications

(4 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Continuum Model (PCM) [76], which includes both electrostatic and non-electrostatic (cavity and dispersion) solvation terms, selecting ethanol as the condensed phase because its dielectric constant (=24.852) is close to that of glucose at high temperature. Since the thermochemical conversion of cellulose in supercritical water conditions has been previously studied in the frame of hydrothermal carbonization/liquefaction processes [77,78], we also considered supercritical water (SCW) conditions. Within the context of the SMD solvation model, the SCW conditions can be approximated by properly adjusted parameters.…”

Section: Pcm Calculationsmentioning

confidence: 99%

Pyrolytic Conversion of Glucose into Hydroxymethylfurfural and Furfural: A Survey of Mechanisms and Benchmark Quantum-Chemical Calculations

López,

Suárez

2023

Preprint

View full text Add to dashboard Cite

Quantum chemical methods have been intensively applied to study the pyrolytic conversion of glucose into hydroxymethylfurfural (HMF) and furfural (FF). Herein, we collect the most relevant mechanistic proposals from the recent literature and organize them into a single reaction network. The transition structures (TSs) and intermediates are characterized using high level ab initio methods that predict relative energies within chemical accuracy. The reaction pathways are assessed in terms of the Gibbs free energy differences of the TSs and intermediates with respect to β-glucopyranose, selecting a 2D ideal-gas standard state at 773K to represent the usual pyrolysis conditions. After having scored all the possible pathways throughout the network assuming reversible reaction steps, several pathways, which present various changes with respect to the former proposals, can lead to the formation of both HMF and FF passing through rate-determining TSs that have ∆G‡ values of ~ 49-50 kcal/mol. Interestingly, the catalysis by auxiliary water molecules and the non-specific environmental effects as modelled by solvent continuum methods, have only a minor impact on the Gibbs free energy profiles of the most favoured routes. Since the HMF fragmentation (HMF→FF+CH2O) is predicted to have a small ∆rxnG value and an accessible ∆G‡ barrier, the HMF/FF molecular ratio may be partly determined by equilibrium conditions. In addition, the benchmark energies and structures are employed to study the performance of density functional methodologies. Finally, we show that the computational results are in consonance with the kinetic parameters derived from lumped models, the results of isotopic labelling experiments and the reported HMF/FF molecular ratios. Eventually, they could be useful in future computational studies focused on the kinetic modelling of the pyrolysis mechanisms including non-equilibrium kinetic effects, which could render much more detailed information about product yields and the importance of the various pathways.

show abstract

Section: Pcm Calculationsmentioning

confidence: 99%

Pyrolytic Conversion of Glucose into Hydroxymethylfurfural and Furfural: A Survey of Mechanisms and Benchmark Quantum-Chemical Calculations

López,

Suárez

2023

Preprint

View full text Add to dashboard Cite

show abstract

“…Carbon-based metal-free catalysts have shown promising properties in alkaline environments [ 5 , 6 , 7 ], especially if focusing on the prospect of obtaining a high performance at a fraction of the cost and with widely available resources. These materials also show some obstacles on the path to commercial utilization, with issues related mainly to their long-term stability, selectivity, and kinetics, often in contrast to their noble metal counterparts [ 8 ]. Furthermore, the wide variety of carbon materials, from graphene to carbon nanotubes to amorphous carbons, means that a one-size-fits-all approach is usually not possible [ 9 , 10 , 11 ].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Performance of Metal-Free Carbon-Based Catalysts from Different Hydrothermal Carbonization Treatments for Oxygen Reduction Reaction

Girimonte,

Stefani,

Mucci

et al. 2024

Nanomaterials

View full text Add to dashboard Cite

This research investigates the difference between products obtained through two hydrothermal carbonization treatments. Our aim is to synthesize metal-free, carbon-based catalysts for the oxygen reduction reaction (ORR) to serve as efficient and cost-effective alternatives to platinum-based catalysts. Catalysts synthesized using the traditional hydrothermal approach exhibit a higher electrocatalytic activity for ORR in alkaline media, despite their more energy-intensive production process. The superior performance is attributed to differences in the particle morphology and the chemical composition of the particle surfaces. The presence of functional groups on the surfaces of catalysts obtained via a traditional approach significantly enhances ORR activity by facilitating deprotonation reactions in an alkaline environment. Our research aims to provide a reference for future investigations, shifting the focus to the fine-tuning of surface chemical compositions and morphologies of metal-free catalysts to enhance ORR activity.

show abstract

“…The escalation of heavy metal pollution in the environment can be predominantly attributed to the burgeoning human population and a plethora of anthropogenic activities. These activities encompass diverse sectors such as mining operations and the discharge of both treated and untreated waste effluents containing toxic metals and their derivatives from industries including tanneries, steel plants, battery manufacturing units, and thermal power plants [1,2]. Furthermore, the indiscriminate utilization of fertilizers and pesticides in agricultural practices exacerbates the degradation of water quality by amplifying heavy metal contamination, thereby engendering significant environmental and health concerns [3].…”

Section: Introductionmentioning

confidence: 99%

Removal of Heavy Metal Ions(Fe2+, Mn2+, Cu2+ and Zn2+) on to Activated Carbon Prepared from Kashmiri Walnut Shell (Juglans regia)

Malik,

Khan,

Dar

2024

Univers. J. Green Chem.

View full text Add to dashboard Cite

Heavy metal pollution poses significant threats to the environment and human health, even at trace concentrations. In this study, activated carbon derived from Kashmiri walnut shell (Juglans regia) was investigated for its potential to adsorb heavy metal ions (Fe2+, Mn2+, Cu2+, and Zn2+). Standard solutions containing heavy metal ions at concentrations ranging from 10 to 50 ppm were prepared for adsorption experiments, i.e., at temperature 25 °C, and adsorbent dosage 1 g using a column mechanism. The activated carbon was first treated with 0.1M HCl and 0.5M ammonia solutions, and then washed with demineralised water. Subsequently, the metal ion solutions were passed through the column individually, and the filtrates were analyzed for heavy metal ion presence. The experimental results demonstrated that walnut shell-derived activated carbon exhibited promising adsorption capacity spanning from 0.36 mg/g for Zn2+, 0.5 mg/g for both Mn2+ and Cu2+ and 0.54 mg/g for Fe2+ thus showing the adsorption trend as Fe2+ > Mn2+ = Cu2+ > Zn2+. This study highlights the potential of using walnut shell-derived activated carbon as an effective and cost-efficient method for mitigating heavy metal pollution in contaminated water sources.

show abstract

Water-catalyzed conversion of glucose to small molecules during hydrothermal carbonization: a density functional theory study

Abstract: Hydrothermal carbonization (HTC) holds great promise for the conversion of biomass to biochar and proceeds via the decomposition of soluble carbohydrates and carbohydrate hydrolysates (e.g., glucose) into small-molecule intermediates, which...

Cited by 6 publications

References 47 publications

Pyrolytic Conversion of Glucose into Hydroxymethylfurfural and Furfural: A Survey of Mechanisms and Benchmark Quantum-Chemical Calculations

Pyrolytic Conversion of Glucose into Hydroxymethylfurfural and Furfural: A Survey of Mechanisms and Benchmark Quantum-Chemical Calculations

Electrochemical Performance of Metal-Free Carbon-Based Catalysts from Different Hydrothermal Carbonization Treatments for Oxygen Reduction Reaction

Removal of Heavy Metal Ions(Fe2+, Mn2+, Cu2+ and Zn2+) on to Activated Carbon Prepared from Kashmiri Walnut Shell (Juglans regia)

Contact Info

Product

Resources

About