Iron-catalyzed graphitization of biomass

Thompson, Emma S.; Danks, A. E.; Bourgeois, Laure; Schnepp, Zoë

doi:10.1039/c4gc01673d

Cited by 204 publications

(159 citation statements)

References 26 publications

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“…Hitherto, various natural carbon precursors were investigated, such as sawdust 24,25 and (hydrothermally treated 26−28 ) saccharides. 29 Furthermore, only a few papers have dealt with the metal-catalyzed graphitization of (native) cellulose.…”

Section: Introductionmentioning

confidence: 99%

Base Metal Catalyzed Graphitization of Cellulose: A Combined Raman Spectroscopy, Temperature-Dependent X-ray Diffraction and High-Resolution Transmission Electron Microscopy Study

et al. 2015

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Microcrystalline cellulose (MCC) spheres homogeneously loaded with the nitrate salts of copper, nickel, cobalt, or iron are excellent model systems to establish the temperature at which highly dispersed base metal nanoparticles are formed as well as to establish the temperature at which catalytic graphitization occurs during pyrolysis in the temperature regime T = 500−800°C. Temperature-dependent X-ray diffraction (TD-XRD) and high-resolution transmission electron microscopy (HRTEM) showed that the base metal nanoparticles are smoothly formed from related base metal oxides via carbothermal reduction (fcc copper, T < 500°C; fcc nickel, T < 500°C; fcc cobalt, T = 570°C; bcc iron, T = 700°C). Moreover, it is shown that at distinct temperatures nickel (T ≥ 800°C), cobalt (T ≥ 800°C), and iron (T ≥ 715°C) nanoparticles catalyze the conversion of the amorphous carbon support into ribbons of turbostratic graphitic carbon according to Raman spectroscopy and TD-XRD. Copper, however, was found to be inactive. Furthermore, HRTEM revealed that nickel (500°C ≤ T < 800°C) and cobalt nanoparticles (700°C ≤ T < 800°C) after their initial formation become encapsulated by graphite-like shells prior to the onset of catalytic graphitization. This does not occur in the presence of iron nanoparticles. This distinction is attributed to the temperature required to access iron nanoparticles by carbothermal reduction and their concomitant mobility. Evidence (HRTEM) is provided that for the onset of catalytic graphitization nickel and cobalt nanoparticles first have to escape from their graphite-like shells. Therefore, iron nanoparticles are the most active catalyst. Our results further show that (metastable) metal carbides play a pivotal role in catalytic graphitization. This is demonstrated by the inactivity of copper nanoparticles, the distinct onset temperatures of catalytic graphitization, and the identification of cementite in the case of iron nanoparticles.

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Section: Introductionmentioning

confidence: 99%

Base Metal Catalyzed Graphitization of Cellulose: A Combined Raman Spectroscopy, Temperature-Dependent X-ray Diffraction and High-Resolution Transmission Electron Microscopy Study

et al. 2015

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“…During this process, polymers first decompose to amorphous carbon (AC), after which AC, as the solid carbon source, dissolves in and precipitates out of the catalyst [16][17][18][19][20][21]. The dissolution and precipitation of AC is affected by the thermal treatment temperatures.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, a catalytic thermal treatment synthesis process has been developed for converting renewable biomass and biopolymers to CBNs, where renewable biomass and biopolymers such as sawdust, saccharides, lignosulfonate, and acetic acid lignin are thermally treated at 800 to 1200 • C using transition metal particles and various metal salts as catalysts [13][14][15][16]. Although the catalytic thermal treatment of biopolymers is a green and promising route for the production of CBNs, the low purity of the products and the difficulty of regulating the formation process remain problems, because these biopolymers show heterogeneity in both structure and composition [13].…”

Section: Introductionmentioning

confidence: 99%

Carbon-Based Nanomaterials from Biopolymer Lignin via Catalytic Thermal Treatment at 700 to 1000 °C

Zhang

Yan

et al. 2018

Polymers

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Abstract:We report the preparation of carbon-based nanomaterials from biopolymer kraft lignin via an iron catalytic thermal treatment process. Both the carbonaceous gases and amorphous carbon (AC) from lignin thermal decomposition were found to have participated in the formation of graphitic-carbon-encapsulated iron nanoparticles (GCEINs). GCEINs originating from carbonaceous gases have thick-walled graphitic-carbon layers (10 to 50) and form at a temperature of 700 • C. By contrast, GCEINs from AC usually have thin-walled graphitic-carbon layers (1 to 3) and form at a temperature of at least 800 • C. Iron catalyst nanoparticles started their phase transition from α-Fe to γ-Fe at 700 • C, and then from γ-Fe to Fe 3 C at 1000 • C. Furthermore, we derived a formula to calculate the maximum number of graphitic-carbon layers formed on iron nanoparticles via the AC dissolution-precipitation mechanism.

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“…18, 41 The catalytic graphitization of other biomass like so wood was conducted by Thompson et al 22 and our group 23 recently and both observed graphitized carbon and mesopore formation in the carbonized products. A few key steps for the catalytic graphitization has been proposed: (1) thermal decomposition of iron precursor Fe(NO 3 ) 3 to form iron oxide nanoparticles; (2) carbothermal reduction of iron oxide to produce Fe 3 C nanoparticles.…”

Section: (D)mentioning

confidence: 99%

“…Over the past decade, biomass derived carbon has aroused great interest in the research eld and also nd wide application in energy storage such as sodium ion battery, 18 supercapacitor 19,20 as well as environmental remediation in adsorption based water purication. 16,[21][22][23] Researchers have fabricated carbon adsorbents from various biomass resources, such as cotton, 21 bamboo, 24 vetiver roots, 25 oil palm wood, 26 rattan sawdust, 27 rice husk, 28,29 banana stalk, 30 peanut shell 31 and successfully used them as adsorbents for either heavy metal or organic pollutants removal from polluted water. Adsorbents those are capable of removing both organic and inorganic pollutants are of great interest and practically useful, while very rare work has been reported so far with both capabilities.…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of mesoporous carbon nanocomposites from natural biomass for efficient dye adsorption and selective heavy metal removal

Chen

et al. 2016

RSC Adv.

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Mesoporous carbon with embedded iron carbide nanoparticles was successfully synthesized via a facile impregnation-carbonization method. A green biomass resource, cotton fabric, was used as a carbon precursor and an iron precursor was implanted to create mesopores through a catalytic graphitization reaction. The pore structure of the nanocomposites can be tuned by adjusting the iron precursor loadings and the embedded iron carbide nanoparticles serve as an active component for magnetic separation after adsorption. The microstructure of the nanocomposites was carefully investigated by various characterization techniques including electron microscopy, X-ray diffraction, surface analyzer, magnetic property analyzer and etc. ), these mesoporous nanocomposites show promising applications in pollutant removal from water. The facile material preparation allows convenient scale-up manufacturing with low cost and minimum environmental impact.

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Iron-catalyzed graphitization of biomass

Abstract: Nanostructured graphitic carbon with tunable mesoporosity is synthesized in one step from raw biomass.

Cited by 204 publications

References 26 publications

Base Metal Catalyzed Graphitization of Cellulose: A Combined Raman Spectroscopy, Temperature-Dependent X-ray Diffraction and High-Resolution Transmission Electron Microscopy Study

Base Metal Catalyzed Graphitization of Cellulose: A Combined Raman Spectroscopy, Temperature-Dependent X-ray Diffraction and High-Resolution Transmission Electron Microscopy Study

Carbon-Based Nanomaterials from Biopolymer Lignin via Catalytic Thermal Treatment at 700 to 1000 °C

Facile synthesis of mesoporous carbon nanocomposites from natural biomass for efficient dye adsorption and selective heavy metal removal

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