Analysis of gas chromatography/mass spectrometry data for catalytic lignin depolymerization using positive matrix factorization

Various catalytic technologies are being developed to efficiently convert lignin into renewable chemicals. However, due to its complexity, catalytic lignin depolymerization often generates a wide and complex distribution of product compounds. Gas chromatography/mass spectrometry (GC-MS) is a common analytical technique to profile the compounds that comprise lignin depolymerization products. GC-MS is applied not only to determine the product composition, but also to develop an understanding of the catalytic reaction pathways and of the relationships among catalyst structure, reaction conditions, and the resulting compounds generated. Although a very useful tool, the analysis of lignin depolymerization products with GC-MS is limited by the quality and scope of the available mass spectral libraries and the ability to correlate changes in GC-MS chromatograms to changes in lignin structure, catalyst structure, and other reaction conditions. In this study, the GC-MS data of the depolymerization products generated from organosolv hybrid poplar lignin using a copper-doped porous metal oxide catalyst and a methanol/dimethyl carbonate co-solvent was analyzed by applying a factor analysis technique, positive matrix factorization (PMF). Several different solutions for the PMF model were explored. A 13-factor solution sufficiently explains the chemical changes occurring to lignin depolymerization products as a function of lignin, reaction time, catalyst, and solvent. Overall, seven factors were found to represent aromatic compounds, while one factor was defined by aliphatic compounds

Optimal Design of Passive and Active Control Systems in Seismic-excited Structures Using a New Modified TLBO

Vibration control devices have recently been used in structures subjected to wind and earthquake excitations. The optimal design problems of the passive control device and the feedback gain matrix of the controller for the seismic-excited structures are some attractive problems for researches to develop optimization algorithms with the advancement in terms of simplicity, accuracy, speed, and efficacy. In this paper, a new modified teaching–learning-based optimization (TLBO) algorithm, known as MTLBO, is proposed for the problems. For some benchmark optimization functions and constrained engineering problems, the validity, efficacy, and reliability of the MTLBO are firstly assessed and compared to other optimization algorithms in the literature. The undertaken statistical indicate that the MTLBO performs better and reliable than some other algorithms studied here. The performance of the MTLBO will then be explored for two passive and active structural control problems. It is concluded that the MTLBO algorithm is capable of giving better results than conventional TLBO. Hence, its utilization as a simple, fast, and powerful optimization tool to solve particular engineering optimization problems is recommended

Components of Modernism in Mirzadeh Eshghi's Poetry based on the Strategy of Grounded Theory

Mirzadeh Eshghi is one of the poets of the Constitutional period whose views and opinions are very important in the political and social developments of the Constitutional period. With the aim of identifying the concepts and components of love modernism, the present study intends to answer this main question: What is the pattern of modernism in Mirzadeh Eshghi's poetry collection? His openness, courage, precision, and precise analysis of the political situation of the community are very significant in awakening and stimulating national emotions. The important point is that the lack of attention to the details of modernism, the expression of the diverse themes of modernism and paradoxical thinking, and the inner conflicts of love have caused his thoughts to not be adequately and comprehensively identified; therefore, in this research, using the "Grounded Theory" strategy, without any presumptions and biased judgment, the concepts of modernization in love poems were extracted and categorized. At the end of this process, by comparing and measuring the data and concepts, the components of modernization including 61 concepts were designed and arranged in the form of 11 components. The category of "domestic policy affairs" and Social developments with 12 repetitions have the highest frequency compared to other categories

Effect of plasma treatment on electrochemical performance of lignin-based carbon fibers

The abundant and renewable nature of lignin obtained from wood renders it as a sustainable carbon resource for energy storage applications. However, their environmentally unfavorable processing conditions and limited energy storage performance prohibit the use of lignin-based carbon materials\u27 use as supercapacitor electrodes. The material\u27s properties require advancement to overcome the limitation of low specific capacitances. In this study, we report on the impact on the electrochemical performance of inherently hydrophobic lignin-based carbon fibers (LCF) by subjecting them to a mild plasma treatment. The electrode\u27s capacitance was thus increased by 20%, with better rate capability and energy-power performance (11 Wh/kg and 0.8 kW/kg) in the KOH electrolyte. The quantified improvements were attributed to the capacitive functional groups, and enhanced surface wettability, which increased ion accessibility to active surface area improving charge-transfer ability to the surface with more additional functional groups. Remarkably, the selected plasma conditions introduced mostly desirable functional groups that limited any parasitic faradaic reactions prone to affect the device\u27s long-term cycling stability and self-discharge characteristics. Furthermore, the impact of different inherent and introduced oxygen surface functional groups, including COO−, C[sbnd]OH, C[sbnd]O, and C[dbnd]O, on the capacitive performance of these fibers at different device conditions (such as cycling and electrochemical activation) was investigated in different aqueous electrolytes. To ensure environmental favorability, the electrospinning of lignin fibers was conducted using a high molecular fraction of lignin without the inclusion of any fossil-based co-spinning polymers

From Waste to Wealth: From Kraft Lignin to Free-standing Supercapacitors

Pure eucalyptus Kraft lignin derived carbon fiber mats were produced based on a model workflow. It covers the preparation and characterization of the lignin precursor and the carbon materials and its testing in the final application (supercapacitor). Sequential solvent extraction was employed to produce a eucalyptus Kraft lignin precursor which could be electrospun into lignin fibers without any additives. The fiber formation from low molecular weight lignin is assigned to strong intermolecular interactions via hydrogen bonding and π-π-stacking between individual lignin macromolecules which gives rise to association complexes in the electrospinning solution. By stabilization in air, carbonization in N2 and an activation step in CO2, free-standing microporous carbon fiber mats could be produced. These fiber mats possess mainly basic oxygen functional groups which proved to be beneficial when tested as free-standing electrodes in symmetric supercapacitors. Consequently, the CO2-activated fiber mats showed a high specific gravimetric capacitance of 155 F/g at 0.1 A/g, excellent rate capability with 113 F/g at 250 A/g and good capacitance retention of 94% after 6000 cycles when tested in 6 M KOH electrolyte. Therefore, we conclude that lignin itself is a promising precursor to produce microporous, oxygen functionalized carbon fibers serving as free-standing electrodes in aqueous supercapacitors.We would like to thank EPSRC (EP/R021554/1, EP/N509899/1, EP/P031323/1) for the financial support

A Rapid and Tunable Approach for the Fractionation of Technical Kraft Lignin

Reducing the heterogeneity of technical lignin is essential to obtain predictable and high-performance polymeric materials that are suitable for high-value applications. Organic solvents with different polarities and solubilities can be used to fractionate lignin and reduce the complexity and diversity of its chemical structure. Among the various solvents and solvent mixtures, acetone–water mixtures offer an energy-efficient, cost-effective, and environmentally friendly means of lignin fractionation. In the present study, temperature-induced acetone–water fractionation was investigated to refine the properties of a technical softwood Kraft lignin, i.e., LignoBoost™ lignin. Relatively mild operating conditions were tested, namely, temperatures of 70–110 °C and autogenous pressure. A factorial experimental design was developed using the Design-Expert® software, and three factors (temperature, time, and acetone concentration) were investigated. It was found that temperature-induced fractionation could increase lignin homogeneity and maintain high lignin solubilization with a short processing time

Lignin-derived electrospun freestanding carbons as alternative electrodes for redox flow batteries

Based on information provided the embargo period/end date is 12 monthsBased on information provided the embargo period/end date is 12 month

Free-standing supercapacitors from Kraft lignin nanofibers with remarkable volumetric energy density

We have discovered a very simple method to address the challenge associated with the low volumetric energy density of free-standing carbon nanofiber electrodes for supercapacitors by electrospinning Kraft lignin in the presence of an oxidizing salt (NaNO₃) and subsequent carbonization in a reducing atmosphere. The presence of the oxidative salt decreases the diameter of the resulting carbon nanofibers doubling their packing density from 0.51 to 1.03 mg cm⁻² and hence doubling the volumetric energy density. At the same time, the oxidative NaNO₃ salt eletrospun and carbonized together with lignin dissolved in NaOH acts as a template to increase the microporosity, thus contributing to a good gravimetric energy density. By simply adjusting the process parameters (amount of oxidizing/reducing agent), the gravimetric and volumetric energy density of the resulting lignin free-standing carbon nanofiber electrodes can be carefully tailored to fit specific power to energy demands. The areal capacitance increased from 147 mF cm⁻² in the absence of NaNO₃ to 350 mF cm⁻² with NaNO₃ translating into a volumetric energy density increase from 949 μW h cm⁻³ without NaNO₃ to 2245 μW h cm⁻³ with NaNO₃. Meanwhile, the gravimetric capacitance also increased from 151 F g⁻¹ without to 192 F g⁻¹ with NaNO

The sustainable materials roadmap

Over the past 150 years, our ability to produce and transform engineered materials has been responsible for our current high standards of living, especially in developed economies. However, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of the economy, energy, and climate. We are at the point where something must drastically change, and it must change now. We must create more sustainable materials alternatives using natural raw materials and inspiration from nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments (LCAs) based on reliable and relevant data to quantify sustainability. We need to seriously start thinking of where our future materials will come from and how could we track them, given that we are confronted with resource scarcity and geographical constrains. This is particularly important for the development of new and sustainable energy technologies, key to our transition to net zero. Currently 'critical materials' are central components of sustainable energy systems because they are the best performing. A few examples include the permanent magnets based on rare earth metals (Dy, Nd, Pr) used in wind turbines, Li and Co in Li-ion batteries, Pt and Ir in fuel cells and electrolysers, Si in solar cells just to mention a few. These materials are classified as 'critical' by the European Union and Department of Energy. Except in sustainable energy, materials are also key components in packaging, construction, and textile industry along with many other industrial sectors. This roadmap authored by prominent researchers working across disciplines in the very important field of sustainable materials is intended to highlight the outstanding issues that must be addressed and provide an insight into the pathways towards solving them adopted by the sustainable materials community. In compiling this roadmap, we hope to aid the development of the wider sustainable materials research community, providing a guide for academia, industry, government, and funding agencies in this critically important and rapidly developing research space which is key to future sustainability.journal articl