☆ 4.4 Article

Theoretical studies on formation mechanisms of CO and CO2 in cellulose pyrolysis

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2011)

Journal

COMPUTATIONAL AND THEORETICAL CHEMISTRY

Volume 964, Issue 1-3, Pages 207-212

Publisher

ELSEVIER SCIENCE BV

DOI: 10.1016/j.comptc.2010.12.027

Keywords

2,3,4-Hydroxyl-butyraldehyde; 2,3,4-Hydroxyl-butyricacid; Decarbonylation; Decarboxylation; Density functional theory (DFT)

Categories

Chemistry, Physical

Funding

National Natural Science Foundation of China [50776101]
Fundamental Research Funds for the Central Universities [CDJX510141150]

Ask authors/readers for more resources

Protocol

Community support

Reagent

Community support

Abstract

In order to understand formation mechanisms of CO and CO2 in cellulose pyrolysis, the pyrolysis of 2,3,4-hydroxyl-butyraldehyde and 2,3,4-hydroxyl-butyricacid as model compounds were investigated by using density functional theory methods at B3LYP/6-31++G(d,p) level. Three possible pyrolytic pathways of each model compound were proposed and geometries of reactants, transition states, intermediates and products were fully optimized. The standard thermodynamic and kinetic parameters of every reaction path in different temperature ranges were calculated. The calculation results show that the releases of CO and CO2 during cellulose pyrolysis are related to the decarbonylation and decarboxylation respectively, and decarbonylation and decarboxylation reactions are concerted processes via intramolecular hydrogen transfer. Decarbonylation are endothermic and decarboxylation are exothermic. The activation energy of decarbonylation of 2,3,4-hydroxyl-butyraldehyde is 294.0 kJ/mol, while the activation energy of decarbonylation of unsaturated olefine aldehyde formed via dehydration of 2,3,4-hydroxyl-butyraldehyde gets increased. The activation energy of decarboxylation of 2,3,4-hydroxyl-butyricacid is 311.7 kJ/mol, while the activation energy of decarboxylation of unsaturated olefine acid formed via dehydration of 2,3,4-hydroxyl-butyricacid gets decreased obviously, which indicates the dehydration favors the release of CO2. (C) 2011 Elsevier B.V. All rights reserved.

Authors

I am an author on this paper

Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.4

Not enough ratings

Secondary Ratings

Novelty

-

Significance

-

Scientific rigor

-

Rate this paper

Recommended

Article Energy & Fuels

An effective strategy for waste oil deoxygenation and upgrading for hydrocarbon biofuels production: A computational and experimental investigation

Feng Long, Xincheng Cao, Xia Jiang, Qaiolong Zhai, Jiaping Zhao, Shitao Yu, Jianchun Jiang, Junming Xu

Summary: Waste oils and other waste materials can be converted into valuable products through pyrolysis, effectively solving the problem of waste disposal. Research shows that pyrolysis conversion of waste oil is a direct and effective deoxygenation method that can be used for producing high-quality biofuels.

JOURNAL OF THE ENERGY INSTITUTE (2022)

Add to Collection

Article Green & Sustainable Science & Technology

Effect of Pd promotion and catalyst support on the Ni-catalyzed deoxygenation of tristearin to fuel-like hydrocarbons

Fei Wang, Robert Pace, Yaying Ji, Jianchun Jiang, Xiaoxiang Jiang, Anna Krystianiak, Olivier Heintz, Gilles Caboche, Eduardo Santillan-Jimenez, Mark Crocker

Summary: In this study, the catalytic activity of Ni catalysts in the decarboxylation/decarbonylation of triglycerides to hydrocarbons was improved by employing Pd as a promoter and using multifunctional supports. Pd addition promoted Ni reduction, leading to an increase in the number of active sites. The use of SiO2-Al2O3 as a support further enhanced the catalyst performance by promoting Ni reduction, as well as providing a high surface area and strong acidity.

RENEWABLE ENERGY (2022)

Add to Collection

Article Engineering, Environmental

Effect of hydroxyl functional groups on SO2 adsorption by activated carbon

Shuhui Zhang, Liwei Wang, Yan Zhang, Fan Cao, Qie Sun, Xiaohan Ren, Ronald Wennersten

Summary: The study explores the influence mechanism of hydroxyl groups on the adsorption of SO2 by activated carbon through experiments and simulations. The results show that hydroxyl functional groups promote the physical adsorption of SO2 on activated carbon by increasing its polarity. The hydroxyl groups also enhance the physisorption of SO2 and H2O through dipole-dipole interactions and hydrogen bonding. The coexistence of SO2, H2O, and O2 on activated carbon promotes their mutual physisorption through non-covalent interactions.

JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING (2022)

Add to Collection

Article Green & Sustainable Science & Technology

Selective production of diesel-like alkanes via Neem seed oil hydrodeoxygenation over Ni/MgSiO3 catalyst

Ali Salehi Zamani, Majid Saidi, Ali Taheri Najafabadi

Summary: In this study, catalytic hydrodeoxygenation (HDO) of Neem seed oil (NSO) over industrial Ni/MgSiO3 catalyst was investigated. The reaction conditions were varied in terms of temperature, pressure, and reaction time to optimize the yield and selectivity towards diesel-like alkanes (C11-C18). The study also explored the effect of catalyst loading on the reaction and evaluated the catalyst efficiency and stability at the optimum condition. The results showed that the DCO2 path was the main reaction mechanism and high yield of diesel-like alkanes (98.60%) was achieved with 20% catalyst loading.

RENEWABLE ENERGY (2023)

Add to Collection

Article Multidisciplinary Sciences

Interpretations of ground-state symmetry breaking and strong correlation in wavefunction and density functional theories

John P. Perdew, Adrienn Ruzsinszky, Jianwei Sun, Niraj K. Nepal, Aaron D. Kaplan

Summary: Strong correlations within a symmetry-unbroken ground-state wavefunction may manifest in approximate density functional theory as symmetry-broken spin densities or total densities, arising from soft modes of fluctuations such as spin-density or charge-density waves. An approximate density functional that breaks symmetry can be more revealing than an exact functional that does not, with examples including the stretched H-2 molecule, antiferromagnetic solids, and the static charge-density wave/Wigner crystal phase of a low-density jellium. Time-dependent density functional theory quantitatively shows that the static charge-density wave is a soft plasmon, with the frequency of a related density fluctuation dropping to zero.

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA (2021)

Add to Collection

Article Chemistry, Physical

Hydrogen adsorption on calcium, potassium, and magnesium-decorations aluminene using density functional theory

Al Rey Villagracia, Hui Lin Ong, Dhan Shemaiah Bayasen, Hsin Lin, Melanie David, Nelson Arboleda

Summary: The study introduced impurities such as calcium, potassium, and magnesium into planar aluminene, finding that these interstitial dopants can affect hydrogen adsorption behavior, enhancing hydrogen storage performance. This chemisorption was validated by density functional theory, demonstrating the potential of these materials for hydrogen storage.

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (2021)

Add to Collection

Article Chemistry, Physical

Recent advancement in deoxygenation of fatty acids via homogeneous catalysis for biofuel production

Mojtaba Tabandeh, Chin Kui Cheng, Gabriele Centi, Pau Loke Show, Wei-Hsin Chen, Tau Chuan Ling, Hwai Chyuan Ong, Eng-Poh Ng, Joon Ching Juan, Su Shiung Lam

Summary: The methods of producing biofuels can be done through homogeneous and heterogeneous catalysis, with radical-based reactions and transition metal catalysis showing the most promising results, being more active and selective in decarboxylation and decarbonylation of fatty acids.

MOLECULAR CATALYSIS (2022)

Add to Collection

Article Energy & Fuels

Simulation of deoxygenation of vegetable oils for diesel-like fuel production in continuous reactor

Gisele Cristina Rabelo Silva, Maria Helena Cano de Andrade

Summary: This study proposes a model for deoxygenation of vegetable oil components in the manufacturing process of renewable diesel. By evaluating the conversion of triglycerides over the deoxygenation catalyst with rigorous kinetic data, the study analyzes the influence of reactor pressure, temperature, and H2/oil molar ratio, as well as the type of feedstocks. The model can be used for new product design, improving operation conditions, and economic analysis in green diesel manufacturing.

BIOMASS CONVERSION AND BIOREFINERY (2023)

Add to Collection

Article Chemistry, Organic

Pd/LA-catalyzed decarboxylation enabled exclusive [5+2] annulation toward N-aryl azepanes and DFT insights

Teng Liu, Yuqi Fang, Linhong Zuo, Yulian Yang, Yin Liu, Weipeng Chen, Li Dang, Wusheng Guo

Summary: A practical and straightforward methodology for synthesizing non-fused N-aryl azepane derivatives with diversity has been described. The reactions proceed smoothly under mild conditions with CO2 as a byproduct, and the resulting products can be easily converted into a range of highly functionalized azepanes. The DFT calculations reveal the details of the reaction pathway and the origin of the unusual exclusive [5 + 2] annulation process.

ORGANIC CHEMISTRY FRONTIERS (2021)

Add to Collection

Article Chemistry, Physical

Effects of Co-adsorbed Water on Different Bond Cleavages of Oxygenates on Pd (111)

Kingsley C. Chukwu, Liney Arnadottir

Summary: Co-adsorbed water generally enhances O-H bond cleavage while inhibiting OC-O, C-C, and OC-OH bond cleavage on metal surfaces. The influence of co-adsorbed water on C-H bond cleavage varies and depends on the nature of the transition state. The presence of co-adsorbed water can lead to more favorable formation of carbon dioxide over carbon monoxide in the decomposition of acetic acid on Pd (111).

ACS CATALYSIS (2022)

Add to Collection

Article Engineering, Environmental

Density Functional Theory Calculations Decipher Complex Reaction Pathways of 6:2 Fluorotelomer Sulfonate to Perfluoroalkyl Carboxylates Initiated by Hydroxyl Radical

Yanyan Zhang, Jinxia Liu, Subhasis Ghoshal, Audrey Moores

Summary: In this study, the reaction path of 6:2 FTSA initiated by (OH)-O-center dot was mapped using density functional theory (DFT) calculations and experimentally verified. It was found that the parallel addition of (OH)-O-center dot and O-2 to CnF2n+1 center dot was essential to producing C2-C6 PFCAs. The generation of alkoxyl radicals and chain cleavage were identified as critical steps in the transformation process.

ENVIRONMENTAL SCIENCE & TECHNOLOGY (2021)

Add to Collection

Article Chemistry, Physical

The electronic properties and structural stability of LaFeO3 oxide by niobium doping: A density functional theory study

Yongjun Zhou, Zhe Lu, Jingwei Li, Shifeng Xu, Dan Xu, Bo Wei

Summary: This study investigated the electronic properties and structural stability of Nb-doped LaFeO3 oxide, as well as the adsorption of H-2 molecule on both clean and Nb-doped LFO surfaces through theoretical calculations. The results showed that Nb doping improved electrical conductivity and enhanced structural stability of orthorhombic LFO, providing a theoretical explanation for experimental observations. Additionally, Nb doping slightly enhanced the adsorption of H-2 molecule and facilitated the dissociation of H-2 to H atoms.

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (2021)

Add to Collection

Review Energy & Fuels

A review on the production and physicochemical properties of renewable diesel and its comparison with biodiesel

Rashi Koul, Naveen Kumar, R. C. Singh

Summary: Renewable diesel, produced through hydrotreating of triglycerides in vegetable oil, is a promising substitute for traditional diesel with high cetane index and good cold flow properties.

ENERGY SOURCES PART A-RECOVERY UTILIZATION AND ENVIRONMENTAL EFFECTS (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Decarbonylation and decarboxylation of propanoic acid on Pd55 clusters: a quantum chemical modeling

R. S. Shamsiev

Summary: The reaction mechanisms of the decarbonylation and decarboxylation of propanoic acid on Pd-55 icosahedral and cuboctahedral clusters were studied using density functional theory. The results showed that the hydrogen abstraction step in the decarboxylation reaction is highly sensitive to the cluster shape and is more favorable on the icosahedral cluster. The icosahedral cluster also exhibited higher activity and selectivity towards decarboxylation compared to the cuboctahedral cluster.

RUSSIAN CHEMICAL BULLETIN (2022)

Add to Collection

Article Chemistry, Physical

Abundant oxygen vacancies promote bond breaking of hydrogen peroxide on 3D urchin-like Pd/W18O49 surface to achieve high-performance catalysis of hydroquinone oxidation

Changding Wang, Yu Lei, Qiaoya Lv, Pinyi Wang, Weiping Kong, Fu Wan, Weigen Chen

Summary: This study reports a new high-quality catalyst composed of a trace amount of silver-supported 3D urchin-like Pd/W18O49 composite. The catalyst exhibits efficient catalytic oxidation of hydroquinone in aqueous solution, surpassing commercial catalysts. Experimental and theoretical analysis reveals that the excellent performance of this catalyst is mainly attributed to the electronic induction effect between W18O49 and Pd nanoparticles, as well as the oxygen vacancies on the surface of W18O49.

APPLIED CATALYSIS B-ENVIRONMENTAL (2022)

Add to Collection

No Data Available

Article Chemistry, Physical

Exploring the antiviral potency of γ-FP and PA compounds: Electronic characterization, non-covalent interaction analysis and docking profiling with emphasis on QTAIM aspects

A. Aathif Basha, Attar Kubaib, Mohammad Azam

Summary: The properties of a set of compounds were comprehensively assessed using various analytical techniques, revealing their stability and favorable drug-like characteristics. Potential antiviral and antioxidant properties were predicted, indicating promise for biological efficacy.

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2024)

Add to Collection

Article Chemistry, Physical

Effect of number of donor-acceptor repeat units and macrocyclic configuration on excited state properties in TADF emitters: A multiscale theoretical study

Meiqi Liu, Baoming Hou, Yuheng Li, Yuyu Pan, Bing Yang

Summary: This paper investigates the application potential of thermally activated delayed fluorescent (TADF) molecules with donor-acceptor-donor-acceptor pi-conjugated macrocycle structures in organic light-emitting diodes. The study finds that the macrocyclic structure has a smaller energy gap between the first singlet excited state and the first triplet excited state compared to the linear structure. The TADF efficiency is also analyzed and explained based on spin-orbit coupling and intersystem crossing rates.

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2024)

Add to Collection

Article Chemistry, Physical

Remodeling and adsorption behavior of Co2+-doped SnO2 (221) crystal plane by H2O molecules

Run Liu, Jiahui Liu, Jiarui Fang, Xiruo Bai, Dan Wang, Yixuan Qie, Shuqi Zu, Guancheng Wang, Xinyi Sui, Runyao Chang, Yizhu Wang, Ziheng Li

Summary: This paper investigates the remodeling effect of H2O molecules and their adsorption behavior on Co2+-doped SnO2 (221) crystal plane materials. The results show that H2O molecules remodel the crystal plane by creating oxygen defects, leading to hydroxylation. The hydroxylated crystal surface adsorbs O2 and then H2O molecules, affecting the electrical conductivity of the crystal plane.

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2024)

Add to Collection

Article Chemistry, Physical

Metal-adorned borophene for efficient glucose adsorption

Marisol Ibarra-Rodriguez, Paul Horley, Mario Sanchez

Summary: In this study, the functionalized borophene was investigated as a potential sensor or transporter of glucose for biomedical applications. The adsorption of glucose molecules on different boron-based complexes was studied, and the results showed that these complexes have high binding energies and can efficiently adsorb glucose molecules. The findings suggest that borophene-based systems with different oxidation states hold promise for intelligent drug delivery and biosensor design.

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2024)

Add to Collection

Article Chemistry, Physical

Computational study on Thermal and morphological characteristics of Carbazochrome encapsulation capacity in Carbon nanotube

Syed Hassan Sarwar, Saad Jawaid Khan, Syed Faraz Jawed

Summary: The medical community is currently focusing on targeted and controlled drug delivery, and many researchers are utilizing computational resources to understand drugnanocarrier combinations and develop targeted drug delivery systems. This study used molecular dynamics to investigate the encapsulation capacity of Carbazochrome, a hemostatic drug, in Single-Walled Carbon Nanotubes of different morphological variations. The results showed that the nanotube radius and length had the most significant impact on the encapsulation capacity, followed by nanotube chirality. Temperature also affected the drug encapsulation when the nanotube radius was not very large and the chiral angle was near 30 degrees.

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2024)

Add to Collection

Article Chemistry, Physical

DFT study of B substitution on the hydrogen storage properties of pt-modified conical cup-stacked carbon nanotube

Yinquan Sui, Mengying Sun, Yongxin Wang, Zhitong Xu, Jinglu Yan, Huanpeng Liu

Summary: In this study, the structural and hydrogen storage properties of loaded Pt atoms were investigated using density functional theory (DFT) with and without substitution of B atoms on the edges of conical graphene layers (CGL). It was found that the position of the substituted B atom at the edge of the CGL has an important effect on the position of the loaded Pt atom and its hydrogen adsorption and storage properties.

COMPUTATIONAL AND THEORETICAL CHEMISTRY (2024)

Add to Collection

© Peeref 2019-2024. All rights reserved.