Tuning thermal and graphitization behaviors of lignin via complexation with transition metal ions for the synthesis of multilayer graphene-based materials.

Thermal conversion of kraft lignin, an abundant renewable aromatic substrate, into advanced carbon materials including graphitic carbon and multilayer/turbostratic graphene has recently attracted great interest. Our innovative catalytic upgrading approach integrated with molecular cracking and welding (MCW) enables mass production of lignin-derived multilayer graphene-based materials. To understand the critical role of metal catalysts in the synthesis of multilayer graphene, this study was focused on investigating the effects of transition metals (i.e., molybdenum (Mo), nickel (Ni), copper (Cu), and iron (Fe)) on thermal and graphitization behaviors of lignin. During the preparation of metal-lignin (M-lignin) complexes, Fenton-like reactions were observed with the formation of Fe- and Cu-lignin complexes, while Ni ions strongly interacted with oxygen-containing surface functional groups of lignin and Mo oxyanions weakly interacted with lignin through ionic bonding. Different chelation mechanisms of transition metal ions with lignin influenced the stabilization, graphitization, and MCW steps involved in thermal upgrading. The M-lignin complex behaviors in each of the three steps were characterized. It was found that multilayer graphene-based materials with nanoplatelets can be obtained from the Fe-lignin complex via MCW operation at 1000 °C under methane (CH4). Raman spectra indicated that Fe- and Ni-lignin complexes experienced a higher degree of graphitization than Cu- and Mo-lignin complexes during thermal treatment.

Production of COx-Free Hydrogen and Few-Layer Graphene Nanoplatelets by Catalytic Decomposition of Methane over Ni-Lignin-Derived Nanoparticles.

Nickel (Ni)-lignin nanocomposites were synthesized from nickel nitrate and kraft lignin then catalytically graphitized to few-layer graphene-encapsulated nickel nanoparticles (Ni@G). Ni@G nanoparticles were used for catalytic decomposition of methane (CDM) to produce COx-free hydrogen and graphene nanoplatelets. Ni@G showed high catalytic activity for methane decomposition at temperatures of 800 to 900 °C and exhibited long-term stability of 600 min time-on-stream (TOS) without apparent deactivation. The catalytic stability may be attributed to the nickel dispersion in the Ni@G sample. During the CDM reaction process, graphene shells over Ni@G nanoparticles were cracked and peeled off the nickel cores at high temperature. Both the exposed nickel nanoparticles and the cracked graphene shells may participate the CDM reaction, making Ni@G samples highly active for CDM reaction. The vacancy defects and edges in the cracked graphene shells serve as the active sites for methane decomposition. The edges are continuously regenerated by methane molecules through CDM reaction.

A Study of the Key Factors on Production of Graphene Materials from Fe-Lignin Nanocomposites through a Molecular Cracking and Welding (MCW) Method.

In this work, few-layer graphene materials were produced from Fe-lignin nanocomposites through a molecular cracking and welding (MCW) method. MCW process is a low-cost, scalable technique to fabricate few-layer graphene materials. It involves preparing metal (M)-lignin nanocomposites from kraft lignin and a transition metal catalyst, pretreating the M-lignin composites, and forming of the graphene-encapsulated metal structures by catalytic graphitization the M-lignin composites. Then, these graphene-encapsulated metal structures are opened by the molecule cracking reagents. The graphene shells are peeled off the metal core and simultaneously welded and reconstructed to graphene materials under a selected welding reagent. The critical parameters, including heating temperature, heating time, and particle sizes of the Fe-lignin composites, have been explored to understand the graphene formation mechanism and to obtain the optimized process parameters to improve the yield and selectivity of graphene materials.

Effect of Solvents on Fe-Lignin Precursors for Production Graphene-Based Nanostructures.

Kraft lignin was catalytically graphitized to graphene-based nanostructures at high temperature under non-oxidative atmospheres. To obtain the best catalytic performance, a uniform catalyst-lignin mixture must be made by bonding transitional metal (M) ions to oxygen (O), sulfur (S) or nitrogen (N)-containing functional groups in kraft lignin. One of the strategies is to dissolve or disperse kraft lignin in a suitable solvent, whereby the polymer chains in the condensed lignin molecules will be detangled and stretched out while the functional groups are solvated, and when mixing lignin solution with catalyst metal solution, the solvated metal ions in an aqueous solution can diffuse and migrate onto lignin chains to form M-O, M-S, or M-N bonds during the mixing process. Therefore, solvent effects are important in preparing M-lignin mixture for production of graphene-based nanostructures. Fe-lignin precursors were prepared by dissolving lignin with different solvents, including water, methanol, acetone, and tetrahydrofuran (THF). Solvent effects on the catalytic performance, size and morphology of graphene-based nanostructures were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HRTEM), and nitrogen sorption measurements. The sizes, morphologies, and catalytic properties of the products obtained from Fe-lignin precursors are greatly influenced by the solvents used. It was found that Fe-lignin (THF) had the highest iron dispersion and the smallest iron particle size. Furthermore, Fe-lignin (THF) exhibited the best catalytic performance for graphitization of kraft lignin while the graphitization degree decreased in the order: Fe-lignin(THF) > Fe-lignin(Acetone) > Fe-lignin(methanol) > Fe-lignin(water).

Efficient Conversion of Lignin Waste to High Value Bio-Graphene Oxide Nanomaterials.

Lignin graphene oxide was oxidized after Kraft lignin was graphitized by thermal catalytic conversion. The reduced lignin graphene oxide was derived from lignin graphene oxide through thermal reduction treatment. These Kraft lignin, lignin graphite, lignin graphene oxide, and reduced lignin graphene oxide were characterized by scanning electron microscopy, raman microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, atomic force microscopy and thermogravimetric analysis. The results showed lignin graphite converted from Kraft lignin had fewer layers with smaller lateral size than natural graphite. Moreover, lignin graphene oxide was successfully produced from lignin graphite by an oxidation reaction with an hour-long reaction time, which has remarkably shorter reaction time than that of graphene oxide made from natural graphite. Meanwhile, this lignin-derived graphene oxide had the same XRD, FTIR and Raman peaks as graphene oxide oxidized from natural graphite. The SEM, TEM, and AFM images showed that this lignin graphene oxide with 1⁻3 average layers has a smaller lateral size than that of graphene oxide made from natural graphite. Moreover, the lignin graphene oxide can be reduced to reduced lignin graphene oxide to fabricate graphene-based aerogel, wire, and film for some potential applications.

Synthetic Bio-Graphene Based Nanomaterials through Different Iron Catalysts.

Kraft lignin was catalytically graphitized to graphene-based nanostructures at 1000 °C under argon atmosphere with four iron catalysts, iron(III) nitrate (Fe-N); iron(II) chloride (Fe-Cl2); iron(III) chloride (Fe-Cl3); and iron(II) sulfate (Fe-S). The catalytic decomposition process of iron-promoted lignin materials was examined using thermalgravimetric analysis and temperature-programmed decomposition methods. The crystal structure, morphology and surface area of produced materials were characterized by means of X-ray diffraction, Raman, scanning electron microscopy, high resolution transmission electron microscopy and N2 adsorption-desorption techniques. Experimental results indicated that iron nitrate catalyst had better iron dispersion three other iron salts. Iron nitrate was the most active catalyst among four iron salts. The low activity of iron in iron chloride-promoted samples was because the residual chlorine over iron surfaces prevent iron interaction with lignin functional groups.

Catalysts on Formation of Carbon-Encapsulated Iron Nanoparticles from Kraft Lignin.

Effects of physical and chemical states of iron-based catalysts on the formation of carbon-encapsulated iron nanoparticles (CEINs) synthesized thermally from kraft lignin were investigated. Experimental results indicated that if solution-based iron nitrate (FeN) was used as an iron source for the catalyst, CEINs observed were α-Fe and γ-Fe-based cores encapsulated by few layers graphitic-carbon (mostly 1-5 layers) and the majority of these CEINs were embedded in amorphous carbon matrix. The formation of graphitic-carbon shells is believed based on the dissolution and precipitation mechanism of amorphous carbon acting as the carbon source. If solid-based iron nanoparticles (FePs) were used as the catalyst, CEINs observed were α-Fe, γ-Fe, and Fe3C-based cores encapsulated with tangled graphitic-carbon nanoribbons and carbon tubules and the majority of these CEINs were found along the edge of amorphous carbon matrix. The growth of tangled graphitic-carbon nanoribbons and carbon tubules is based on a chemical vapor decomposition process, i.e., the carbonaceous gases from kraft lignin decomposition served as the carbon source.

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

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 Fe3C 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.

Thermal Decomposition of Kraft Lignin under Gas Atmospheres of Argon, Hydrogen, and Carbon Dioxide.

The behaviors of thermal decomposition of kraft lignin under three different gases (Ar, CO2, or H2) were analyzed and compared using a temperature-programmed decomposition-mass spectrometry (TPD-MS) system. Experimental results indicated that Ar atmosphere produced the highest yield of solid chars, while H2 atmosphere generated the highest yield of liquids and CO2 atmosphere had the highest yield of gases. TPD-MS results showed that H2 atmosphere was consumed at the temperature range from 205 to 810 °C and CO2 atmosphere was consumed at the temperature range from 185 to 1000 °C. The H2 promoted the cleavage of lignin side chains and significantly enhanced the formation of CH4, C6H6, HCHO, C6H5OH, CH3OH, and tars. The percentages of water in produced liquids were 90.1%, 85.3%, and 95.5% for Ar, H2, and CO2 as atmosphere, respectively. The H2 yielded more organic chemicals in produced liquids compared to the other two gases. The observed organic chemicals were mainly acetic acid, phenols, ketones, alcohols, aldehydes, and esters. BET surface areas of solid products were 11.3, 98.5, and 183.9 m²/g for Ar., H2, and CO2 as the atmosphere, respectively. C⁻H⁻O⁻N⁻S elemental and morphology analyses on solid products indicated that the lowest carbon content and the highest oxygen content were obtained if Ar atmosphere was used, while H2 and CO2 yielded more carbon in final solid products. Solid products obtained under CO2 or H2 atmosphere contained sphere-shaped nanoparticles.

Carbon Nanostructure of Kraft Lignin Thermally Treated at 500 to 1000 °C.

Kraft lignin (KL) was thermally treated at 500 to 1000 °C in an inert atmosphere. Carbon nanostructure parameters of thermally treated KL in terms of amorphous carbon fraction, aromaticity, and carbon nanocrystallites lateral size (La), thickness (Lc), and interlayer space (d002) were analyzed quantitatively using X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy. Experimental results indicated that increasing temperature reduced amorphous carbon but increased aromaticity in thermally treated KL materials. The Lc value of thermally treated KL materials averaged 0.85 nm and did not change with temperature. The d002 value decreased from 3.56 Å at 500 °C to 3.49 Å at 1000 °C. The La value increased from 0.7 to 1.4 nm as temperature increased from 500 to 1000 °C. A nanostructure model was proposed to describe thermally treated KL under 1000 °C. The thermal stability of heat treated KL increased with temperature rising from 500 to 800 °C.

Catalytic removal of oxygen from biomass-derived syngas.

Selective oxygen (O2) removal from wood-derived syngas was investigated over three types of ceria-modified alumina supported metal catalysts (i.e., Pt, Pd, and Cu). Complete O2 removal was observed with the Pt and Pd catalysts at a lower temperature than with the Cu catalyst. Gas hourly space velocity (GHSV) was another critical parameter affecting O2 removal, substantially reducing O2 conversion by all three catalysts at 4000 h(-1) or above. The Cu catalyst appeared to be most sensitive to GHSV. Among three catalysts, the Pd catalyst had the best performance on O2 removal. In addition to reaction conditions, CO2 and water vapor in the syngas also influenced O2 removal, both of which had adverse effects on O2 conversion. Stability tests indicated that both Pt and Pd catalysts were quite stable over a 300 h testing period while the Cu catalyst was deactivated after 50h and regenerated by elevating reaction temperature.

Catalytic conversion wood syngas to synthetic aviation turbine fuels over a multifunctional catalyst.

A continuous process involving gasification, syngas cleaning, and Fischer-Tropsch (FT) synthesis was developed to efficiently produce synthetic aviation turbine fuels (SATFs). Oak-tree wood chips were first gasified to syngas over a commercial pilot plant downdraft gasifier. The raw wood syngas contains about 47% N(2), 21% CO, 18% H(2), 12% CO(2,) 2% CH(4) and trace amounts of impurities. A purification reaction system was designed to remove the impurities in the syngas such as moisture, oxygen, sulfur, ammonia, and tar. The purified syngas meets the requirements for catalytic conversion to liquid fuels. A multi-functional catalyst was developed and tested for the catalytic conversion of wood syngas to SATFs. It was demonstrated that liquid fuels similar to commercial aviation turbine fuels (Jet A) was successfully synthesized from bio-syngas.

Optical fiber evanescent wave absorption spectrometry of nanocrystalline tin oxide thin films for selective hydrogen sensing in high temperature gas samples.

SnO(2) nanocrystalline material was prepared with a sol-gel process and thin films of the nanocrystalline SnO(2) were coated on the surface of bent optical fiber cores for gas sensing. The UV/vis absorption spectrometry of the porous SnO(2) coating on the surface of the bent optical fiber core exposed to reducing gases was investigated with a fiber optical spectrometric method. The SnO(2) film causes optical absorption signal in UV region with peak absorption wavelength at around 320 nm when contacting H(2)-N(2) samples at high temperatures. This SnO(2) thin film does not respond to other reducing gases, such as CO, CH(4) and other hydrocarbons, at high temperatures within the tested temperature range from 300 degrees C to 800 degrees C. The response of the sensing probe is fast (within seconds). Replenishing of the oxygen in tin oxide was demonstrated by switching the gas flow from H(2)-N(2) mixture to pure nitrogen and compressed air. It takes about 20 min for the absorption signal to decrease to the baseline after the gas sample was switched to pure nitrogen, while the absorption signal decreased quickly (in 5 min) to the baseline after switching to compressed air. The adhesion of tin oxide thin films is found to be improved by pre-coating a thin layer of silica gel on the optical fiber. Adhesion increases due to increase interaction of optical fiber surface and the coated silica gel and tin oxide film. Optical absorption spectra of SnO(2) coating doped with 5 wt% MoO(3) were observed to change and red-shifted from 320 nm to 600 nm. SnO(2) thin film promoted with 1 wt% Pt was found to be sensitive to CH(4) containing gas.