Lignin-Based Porous Supraparticles for Carbon Capture.
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ABSTRACT: Multiscale carbon supraparticles (SPs) are synthesized by soft-templating lignin nano- and microbeads bound with cellulose nanofibrils (CNFs). The interparticle connectivity and nanoscale network in the SPs are studied after oxidative thermostabilization of the lignin/CNF constructs. The carbon SPs are formed by controlled sintering during carbonization and develop high mechanical strength (58 N·mm-3) and surface area (1152 m2·g-1). Given their features, the carbon SPs offer hierarchical access to adsorption sites that are well suited for CO2 capture (77 mg CO2·g-1), while presenting a relatively low pressure drop (∼33 kPa·m-1 calculated for a packed fixed-bed column). The introduced lignin-derived SPs address the limitations associated with mass transport (diffusion of adsorbates within channels) and kinetics of systems that are otherwise based on nanoparticles. Moreover, the carbon SPs do not require doping with heteroatoms (as tested for N) for effective CO2 uptake (at 1 bar CO2 and 40 °C) and are suitable for regeneration, following multiple adsorption/desorption cycles. Overall, we demonstrate porous SP carbon systems of low cost (precursor, fabrication, and processing) and superior activity (gas sorption and capture).
Project description:In this work, we reported a new method to fabricate flexible carbon-based supercapacitor electrodes derived from a commercialized and low-cost lignin. The fabrication process skips traditional stabilization/carbonization/activation for lignin-based carbon production. Also, the process reported here was green and facile, with minimum solvent use and no pretreatment required. Characterization of the lignin showed that it has common properties among all types of lignin. The lignin was impregnated on carbon cloth and then subjected to direct laser writing to form the desired electrodes (LLC). The results showed that lignin was successfully bonded to carbon cloth. The LLC has a good porous carbon structure with a high I G/I D ratio of 1.39, and a small interlayer spacing d 002 of 0.3436 nm, which are superior to most of the reported lignin-based carbons. Although not optimized, the fabricated LLC showed good supercapacitance behavior with an areal capacitance of 157.3 mF cm-2 at 0.1 mA cm-2. In addition, the superior flexibility of LLC makes it a promising electrode that can be used more widely in portable devices. Conceptually, this method can be generalized to all types of lignin and can define intriguing new research interests towards lignin applications.
Project description:Through a solution method utilizing benzoxazine chemistry, heteroatoms containing porous carbons (HCPCs) were synthesized from melamine, eugenol and formaldehyde, followed by carbonization in a nitrogen atmosphere and chemical activation with KOH at three different activation temperatures, 700, 800 and 900 °C. The introduction of melamine and eugenol to the monomer produced structurally bonded nitrogen and oxygen in porous carbons. Changing the calcination temperature can alter the doping level of heteroatoms and the particle size. These carbon materials exhibit large pore size distributions, tunable pore structure, high nitrogen and oxygen contents and high surface areas, which make them suitable for use as electrode materials in supercapacitors. As a result of activating at 800 °C, the sample HCPC-800 exhibits a high specific surface area of 984 m2/g, high oxygen and nitrogen content (3.64-6.26 wt.% and 10.61-13.65 wt.%), hierarchical pore structure, high degree of graphitization and good electrical conductivity. An outstanding rate capability is also demonstrated, as well as incredible longevity, retaining the capacitance up to 83% even after 5000 cycles in a solution containing 1 M H2SO4. Moreover, the activated porous carbon containing nitrogen exhibits a CO2 adsorption capacity of 3.6 and 3.5 mmol/g at 25 °C and 0 °C, respectively, which corresponds to equilibrium pressures of 1 bar.
Project description:To address the issue of global warming and climate change issues, recent research efforts have highlighted opportunities for capturing and electrochemically converting carbon dioxide (CO2). Despite metal doped polymers receiving widespread attention in this respect, the structures hitherto reported lack in ease of synthesis with scale up feasibility. In this study, a series of mesoporous metal-doped polymers (MRFs) with tunable metal functionality and hierarchical porosity were successfully synthesized using a one-step copolymerization of resorcinol and formaldehyde with Polyethyleneimine (PEI) under solvothermal conditions. The effect of PEI and metal doping concentrations were observed on physical properties and adsorption results. The results confirmed the role of PEI on the mesoporosity of the polymer networks and high surface area in addition to enhanced CO2 capture capacity. The resulting Cobalt doped material shows excellent thermal stability and promising CO2 capture performance, with equilibrium adsorption of 2.3 mmol CO2/g at 0 °C and 1 bar for at a surface area 675.62 m2/g. This mesoporous polymer, with its ease of synthesis is a promising candidate for promising for CO2 capture and possible subsequent electrochemical conversion.
Project description:Direct structural information of confined CO2 in a micropore is important for elucidating its specific binding or activation mechanism. However, weak gas-binding ability and/or poor sample crystallinity after guest exchange hindered the development of efficient materials for CO2 incorporation, activation and conversion. Here, we present a dynamic porous coordination polymer (PCP) material with local flexibility, in which the propeller-like ligands rotate to permit CO2 trapping. This process can be characterized by X-ray structural analysis. Owing to its high affinity towards CO2 and the confinement effect, the PCP exhibits high catalytic activity, rapid transformation dynamics, even high size selectivity to different substrates. Together with an excellent stability with turnover numbers (TON) of up to 39,000 per Zn1.5 cluster of catalyst after 10 cycles for CO2 cycloaddition to form value-added cyclic carbonates, these results demonstrate that such distinctive structure is responsible for visual CO2 capture and size-selective conversion.
Project description:The preparation of nitrogen-doped activated carbon (NACs) has received significant attention because of their applications in CO2 capture and sequestration (CCS) owing to abundant nitrogen atoms on their surface and controllable pore structures by carefully controlled carbonization. We report high-surface-area porous N-doped activated carbons (NAC) by using soft-template-assisted self-assembly followed by thermal decomposition and KOH activation. The activation process was carried out under different temperature conditions (600-800 °C) using polyimine as precursor. The NAC-800 was found to have a high specific surface area (1900 m2 g-1), a desirable micropore size below 1 nm and, more importantly, a large micropore volume (0.98 cm3 g-1). NAC-800 also exhibits a significant capacity of CO2 capture i.e., over 6. 25 and 4.87 mmol g-1 at 273 K and 298 K respectively at 1.13 bar, which is one of among the highest values reported for porous carbons so far. Moreover, NAC also shows an excellent separation selectivity for CO2 over N2.
Project description:The renewable resource as a major feedstock to prepare porous carbon has showed many advantages compared to fossil-based materials. This study proposes a new strategy to synthesize palladium nanoparticles (Pd NPs)-supported porous carbon, utilizing both the chemical reactivity and the carbon-rich 3D network of lignin. The Pd NPs-supported porous carbons were prepared in one-pot synthesis, with Pd(NH3)2Cl2 as precursor, lignin as reducing and stabilizing agents of Pd NPs, nano SiO2 as hard-template, followed by carbonization and removal of the template. The results reveal a positive effect of Pd precursor dosage on the development and excellent texture of the Pd NPs-supported porous carbon. Accordingly, the synthesized porous carbon was proved to have large micropore volume and good micro-mesopore porous structure, revealing it a promising hydrogen adsorbent.
Project description:Carbon fibers have high surface areas and rich functionalities for interacting with ions, molecules, and particles. However, the control over their porosity remains challenging. Conventional syntheses rely on blending polyacrylonitrile with sacrificial additives, which macrophase-separate and result in poorly controlled pores after pyrolysis. Here, we use block copolymer microphase separation, a fundamentally disparate approach to synthesizing porous carbon fibers (PCFs) with well-controlled mesopores (~10 nm) and micropores (~0.5 nm). Without infiltrating any carbon precursors or dopants, poly(acrylonitrile-block-methyl methacrylate) is directly converted to nitrogen and oxygen dual-doped PCFs. Owing to the interconnected network and the highly optimal bimodal pores, PCFs exhibit substantially reduced ion transport resistance and an ultrahigh capacitance of 66 μF cm-2 (6.6 times that of activated carbon). The approach of using block copolymer precursors revolutionizes the synthesis of PCFs. The advanced electrochemical properties signify that PCFs represent a new platform material for electrochemical energy storage.
Project description:Designing of porous carbon system for CO2 uptake has attracted a plenty of interest due to the ever-increasing concerns about climate change and global warming. Herein, a novel N rich porous carbon is prepared by in-situ chemical oxidation polyaniline (PANI) on a surface of multi-walled carbon nanotubes (MWCNTs), and then activated with KOH. The porosity of such carbon materials can be tuned by rational introduction of MWCNTs, adjusting the amount of KOH, and controlling the pyrolysis temperature. The obtained M/P-0.1-600-2 adsorbent possesses a high surface area of 1017 m2 g-1 and a high N content of 3.11 at%. Such M/P-0.1-600-2 adsorbent delivers an enhanced CO2 capture capability of 2.63 mmol g-1 at 298.15 K and five bars, which is 14 times higher than that of pristine MWCNTs (0.18 mmol g-1). In addition, such M/P-0.1-600-2 adsorbent performs with a good stability, with almost no decay in a successive five adsorption-desorption cycles.
Project description:A series of novel triazine-containing pore-tunable carbon materials (NT-POP@800-1-6), which was synthesized via pyrolysis of porous organic polymers (POPs) without any templates. NT-POP@800-1-6 possess moderate BET surface areas of 475-736?m2?g-1, have permanent porosity and plenty of nitrogen units in the skeletons as effective sorption sites, and display relatively rapid guest uptake of 56-192 wt% in iodine vapour in the first 4?h. In addition, all the samples exhibit the outstanding CO2 adsorption capacity of 2.83-3.96?mmol?g-1 at 273?K and 1.05?bar. Furthermore, NT-POP@800-1-6 show good selectivity ratios of 21.2-36.9 and 3.3-7.5 for CO2/N2 or CH4/N2, respectively. We believe that our new building block design provides a general strategy for the construction of triazine-containing carbon materials from various extended building blocks, thereby greatly expanding the range of applicable molecules.
Project description:The kraft lignin's low molecular weight and too high hydroxyl content hinder its application in bio-based carbon fibers. In this study, we were able to polymerize kraft lignin and reduce the amount of hydroxyl groups by incubating it with the white-rot fungus Obba rivulosa. Enzymatic radical oxidation reactions were hypothesized to induce condensation of lignin, which increased the amount of aromatic rings connected by carbon-carbon bonds. This modification is assumed to be beneficial when aiming for graphite materials such as carbon fibers. Furthermore, the ratio of remaining aliphatic hydroxyls to phenolic hydroxyls was increased, making the structure more favorable for carbon fiber production. When the modified lignin was mixed together with cellulose, the mixture could be spun into intact precursor fibers by using dry-jet wet spinning. The modified lignin leaked less to the spin bath compared with the unmodified lignin starting material, making the recycling of spin-bath solvents easier. The stronger incorporation of modified lignin in the precursor fibers was confirmed by composition analysis, thermogravimetry, and mechanical testing. This work shows how white-rot fungal treatment can be used to modify the structure of lignin to be more favorable for the production of bio-based fiber materials.