Laboratory of Applied Materials for Energy (EnergyLab)

Tracey C.T., Shavronskaya D.O., Shao J., Yang H., Krivoshapkin P.V., Krivoshapkina E.F.

Biodiesel is a petroleum diesel substitute made by reacting oils and fats obtained from plants and animals with short-chain alcohols. The most common approach to biodiesel synthesis is transesterification, which, although a spontaneous reaction, is often catalysed by both homogeneous and heterogeneous catalysts. Homogeneous catalysts, typically very strong acids and bases, have the disadvantages of requiring special equipment and being very difficult to separate from the end product; therefore, heterogeneous catalysts, primarily metal and metal oxide nanoparticles, are preferred. However, conventional heterogeneous catalysts have several limitations, including poor industrial applicability. Recently, carbon-based nanoparticles, including carbon dots (C-dots), have been proposed as potential catalysts. A fledgling innovation, C-dots are a promising heterogeneous catalyst due to their easy, cost-effective synthesis; modifiability; high specific surface area; high specificity; and high conversion efficiency. Furthermore, unlike other catalysts, C-dots do not have to be removed after biodiesel production and can be included as an additive that improves fuel and engine performance and reduces greenhouse gas emission. This mini review aims to highlight the emerging role of C-dots in biodiesel synthesis via transesterification.

Duarte T.A., Pereira R.F., Medronho B., Maltseva E.S., Krivoshapkina E.F., Varela-Dopico A., Taboada P., Fu L., Ferreira R.A., de Zea Bermudez V.

Kryuchkova A., Savin A., Kiseleva A., Dukhinova M., Krivoshapkina E., Krivoshapkin P.

Developing biocompatible, magnetically controlled polymers is a multifunctional solution to many surgical complications. By combining nanoparticle technology with the latest advancements in polymer materials science, we created a multicomponent hybrid system comprised of a robust native spider silk-based matrix; a Mn0.9Zn0.1Fe2O4 nanoparticles coating to provide a controlled thermal trigger for drug release; and liposomes, which act as drug carriers. Fluorescent microscope images show that the dye loaded into the liposomes is released when the system is exposed to an alternating magnetic field due to heating of ferromagnetic nanoparticles, which had a low Curie temperature (40-46°С). The silk matrix also demonstrated outstanding biocompatibility, creating a favorable environment for human postnatal fibroblast cell adhesion, and paving the way for their directed growth. This paper describes a complex approach to cartilage regeneration by developing a spider silk-based scaffold with anatomical mechanical properties for controlled drug delivery in a multifunctional autologous matrix-induced chondrogenesis.

Shavronskaya D.O., Nazarova E.A., Krivoshapkina E.F.

Lactose concentration is a key parameter for assessing the quality of raw and processed milk and identifying abnormal milk. Current methods for lactose determination are laborious, time-consuming and oftentimes require skilled lab workers, expensive equipment, and special reagents. In this study, an optical biosensor system based on nanosized titanium dioxide (TiO2) is presented for routine measurement of lactose in milk without sample preparation. TiO2 was obtained via sol-gel synthesis and characterized using dynamic light scattering, microelectrophoresis, X-ray diffraction, transmission electron microscopy, and nitrogen adsorption-desorption analysis. The system, whose colorimetric response was based on the chromogen-free TiO2-based detection of hydrogen peroxide (H2O2), used β-galactosidase and/or glucose oxidase as the biorecognition elements. The selectivity and sensitivity of the biosensors for lactose and glucose was investigated by diffuse reflectance spectroscopy using standard aqueous lactose and glucose solutions and whole milk samples. The results showed that the proposed biosensors had high optical signal reproducibility (RSD = 5–6%), high sensitivity (LOD = 0.005 wt%), and high selectivity. The linear dynamic ranges of lactose and glucose detection were from 0.005 wt% to 0.100 wt%, and the optimal response time of the biosensor was 25 min. The listed features and advantages of label-free detection make the biosensor attractive for simple, inexpensive, sensitive, and selective determination of lactose in milk.

Medvedev I., Krivoshapkina E., Klinkova A.

We are grateful for the invitation to this session by Prof. Alice H. Suroviec. Electrochemical conversion of CO2 to useful chemicals and synthetic electrochemistry in general are rapidly developing and expanding areas of research and industrial application, which necessitates developing undergraduate curricula that will help students build and retain a strong foundational knowledge in this area of chemistry. Currently, there is a limited set of electrochemistry experiments that undergraduate students are typically exposed to in the laboratory, and synthetic electrochemistry is generally limited to water electroreduction to generate hydrogen gas. As a result, students develop limited knowledge, interest and appreciation of synthetic electrochemistry. At the same time, students today are more inclined to learn about methods and concepts that are important for climate action and sustainable development. With this motivation in mind, we developed a laboratory experiment designed to actively engage students in the learning process and help them understand synthetic electrochemistry through a hands-on experience involving CO2 electroreduction. In general, CO2 electroreduction can yield many different chemicals and requires complex and expensive electrochemical workstation and analytical instrumentation to identify and quantify the products, making it prohibitive for wide adaptation in undergraduate laboratories. Here, we propose a simple and affordable setup that still allows students to directly experience all the necessary steps of the process. The proposed laboratory experiment involves testing the performance of different cathodic electrocatalysts in CO2 reduction reaction conducted in a DIY divided electrochemical cell by measuring the produced CO gas with a CO meter using affordable and broadly available supplies. The students learn the importance of the electrocatalyst composition by changing the material of the cathode and observing different amounts of CO produced or the absence of CO when using the electrode selective for only water reduction. They learn about the influence of the applied potential on the reaction rate by changing the battery voltage and observing the quantitative difference in the produced gas. The experiment is designed to be safe when conducted on a standard laboratory bench (i.e., carbon monoxide concentrations outside of the cell are below the threshold of a standard CO detector).

Osman A.I., Ayati A., Farghali M., Krivoshapkin P., Tanhaei B., Karimi-Maleh H., Krivoshapkina E., Taheri P., Tracey C., Al-Fatesh A., Ihara I., Rooney D.W., Sillanpaä M.

AbstractThe presence of pharmaceuticals in ecosystems is a major health issue, calling for advanced methods to clean wastewater before effluents reach rivers. Here, we review advanced adsorption methods to remove ibuprofen, with a focus on ibuprofen occurrence and toxicity, adsorbents, kinetics, and adsorption isotherms. Adsorbents include carbon- and silica-based materials, metal–organic frameworks, clays, polymers, and bioadsorbents. Carbon-based adsorbents allow the highest adsorption of ibuprofen, from 10.8 to 408 mg/g for activated carbon and 2.5–1033 mg/g for biochar. Metal–organic frameworks appear promising due to their high surface areas and tunable properties and morphology. 95% of published reports reveal that adsorption kinetics follow the pseudo-second-order model, indicating that the adsorption is predominantly governed by chemical adsorption. 70% of published reports disclose that the Langmuir model describes the adsorption isotherm, suggesting that adsorption involves monolayer adsorption.

Dmitrieva A., Medvedev J., Medvedeva K., Krivoshapkina E.F., Klinkova A.

The electrochemical fixation of CO2 by imines has recently attracted an increased interest as sustainable strategy for the synthesis of α-amino acids and a green alternative to the traditional Strecker synthesis, which relies on highly toxic precursors. Despite the industrial prospects of the electrochemical approach, the catalyst material effects on the selectivity of the process are still purely understood, hindering rational catalyst design. Herein, we study the electrochemical fixation of CO2 by N-benzylideneaniline using a wide variety of cathode materials, including 10 polycrystalline metals (Ti, Zn, Au, Pd, Pt, Sn, Ag, Ni, Fe, Cu), glassy carbon, and Pd nanoparticles of different shapes. We found that among all studied bulk metals, Ti and Zn show the best results with above 93% faradaic efficiency of α-amino acid, while other materials show from good to low selectivity (12% for Sn). We also demonstrate that especially high current densities and nearly quantitative faradaic efficiency and selectivity of α-amino acids can be achieved by employing Pd nanoparticles.

Gritsenko M.M., Nazarova E.A., Krivoshapkin P.V., Krivoshapkina E.F.

Hydrogen peroxide (H2O2) and starch are common adulterants in milk. H2O2 is a powerful antimicrobial agent and starch is used to increase the viscosity and nutritional value of diluted milk. Adulterating milk with H2O2 and starch can cause serious health problems; therefore, it is important to detect them, even at very low concentrations. Titanium dioxide (TiO2) is a promising indicator and can be used to create sensors that can quantitatively identify these impurities. The principle of the sensor is based on the colour reaction between H2O2 and TiO2 nanoparticles to form peroxotitanic acid. Nanosized TiO2 was synthesized and investigated by various physicochemical methods, such as DLS, XRD, HRTEM, and N2 sorption analysis. The TiO2-based sensors presented in this work are easily scalable and can detect trace amounts of H2O2 (from 50 ppm) and starch (from 250 ppm) in milk. In addition, the selectivity to other common adulterants and reproducibility of the sensors (RSD = 5–7 %) were evaluated. The proposed sensor includes the development of an electronic device based on the Arduino hardware platform to take accurate automatic measurements.

Koshevaya E.D., Khramov E.V., Svetogorov R.D., Krasnov A.G., Martakov I.S., Shishkin I.I., Krivoshapkina E.F., Krivoshapkin P.V.

Ayati A., Tanhaei B., Beiki H., Krivoshapkin P., Krivoshapkina E., Tracey C.

Over the last decade, the removal of pharmaceuticals from aquatic bodies has garnered substantial attention from the scientific community. Ibuprofen (IBP), a non-steroidal anti-inflammatory drug, is released into the environment in pharmaceutical waste as well as medical, hospital, and household effluents. Adsorption technology is a highly efficient approach to reduce the IBP in the aquatic environment, particularly at low IBP concentrations. Due to the exceptional surface properties of carbonaceous materials, they are considered ideal adsorbents for the IBP removal of, with high binding capacity. Given the importance of the topic, the adsorptive removal of IBP from effluent using various carbonaceous adsorbents, including activated carbon, biochar, graphene-based materials, and carbon nanostructures, has been compiled and critically reviewed. Furthermore, the adsorption behavior, binding mechanisms, the most effective parameters, thermodynamics, and regeneration methods as well as the cost analysis were comprehensively reviewed for modified and unmodified carbonaceous adsorbents. The compiled studies on the IBP adsorption shows that the IBP uptake of some carbon-based adsorbents is significantly than that of commercial activated carbons. In the future, much attention is needed for practical utilization and upscaling of the research findings to aid the management and sustainability of water resource.

Rao G., Shao J., Chen X., Fu L., Zhang X., Zhang J., Wang Q., Krivoshapkin P., Krivoshapkina E., Chen H.

To improve the pore structure of biochar, the H2 yield of gas, and the quality of bio-oil in biomass pyrolysis, a new pyrolysis strategy of co-pyrolyzing bamboo and Zeolitic Imidazolate Frameworks (ZIF-8) at different temperatures and mixing ratios was proposed. Results showed that ZIF-8 blending improved the quality of pyrolytic products. For biochar, the specific surface area was increased tenfold from 49.63 m2/g for raw bamboo to 557.37 m2/g with a 4:1 mass ratio of bamboo to ZIF-8 at 900 °C. And hierarchical porous biochars were formed. For gas, the H2 yield was increased significantly from 4.35 mmol/g (32.84 vol%) for raw bamboo to 7.87 mmol/g (43.73 vol%) with a 4:1 mass ratio of bamboo to ZIF-8 at 900 °C. For bio-oil, ZIF-8 blending promoted the conversion of bamboo to acetic acids, furans, and cyclopentanones, while inhibiting the formation of polyaromatic compounds, showing that ZIF-8 could enhance the secondary cracking of volatiles and promote the branch chain fracture, dehydrogenation, ring-opening and decarbonylation of bamboo. These results indicated that ZIF-8 had excellent effects on bamboo pyrolysis to produce high-value products, and it was enlightening for biomass thermal conversion utilization.

Zhang J., Shao J., Zhang X., Rao G., Krivoshapkin P., Krivoshapkina E., Yang H., Zhang S., Chen H.

Insufficient water stability is an important problem restricting the practical application of metal–organic frameworks (MOFs) in the field of volatile organic compounds (VOCs) adsorption. In this work, a copper(II) benzene-1,3,5-tricarboxylate MOF (Cu-BTC)/biochar composite with improved water stability was obtained by a facile one-pot method for toluene adsorption applications. Different from the traditional regular octahedral configuration, Cu-BTC was scattered on biochar in the form of broccoli-shaped microspheres. The influence of humid air aging on the physiochemical and toluene adsorption properties of Cu-BTC and Cu-BTC/biochar composites under different periods were explored. The results show that the inner structure of Cu-BTC degrades with the micropores transformed into meso-macropores under the humid air aging. Moreover, the BET surface area was reduced by 63.2 % and 94.7 % after 3-month and 6-month aging, respectively, which could eventually lead to a serious decline (76.3 % and 96.5 %) in the adsorption capacities of toluene. It can also be found that compared to traditional octahedral Cu-BTC, the degradation process of broccoli-shaped Cu-BTC/biochar is effectively slowed down, which shows better moisture stability. The retention rates of toluene adsorption capacities for broccoli-shaped Cu-BTC/biochar were 57.7 % and 17.1 % after 3-month and 6-month aging, respectively. This study is helpful for better improving the water stability of MOFs materials used for VOCs adsorption.

Ngo T.S., Tracey C.T., Navrotskaya A.G., Bukhtiyarov A.V., Krivoshapkin P.V., Krivoshapkina E.F.

The last few decades have seen a dramatic increase in heavy metal ions in industrial wastewater, especially Cr6+ and Co2+ ions, which have been shown to adversely affect human health; thus, there is a great need for their removal. Existing removal methods are time-consuming, expensive, and require high technical skills; therefore, there exists a need for a quick, simple, and cost-effective method. Chitin was selected from natural materials (shrimp waste), and an inexpensive, biodegradable, fluorescent carbon dot/chitin nanocrystal (C-dot/ChNC) sorbent for the simultaneous detection and removal of heavy metal ions from wastewater was synthesized from it. C-dot/ChNC shows high selectivity and sensitivity to Cr6+ and Co2+ ions and has high chromium(VI) and cobalt(II) adsorption capacities. These ions are weakly adsorbed on the C-dot/ChNC surface and are easily removed during regeneration, showing high cyclability. Thus, C-dot/ChNC is a viable sorbent for the removal of heavy metal ions during wastewater treatment.

Tracey C.T., Kryuchkova A.V., Bhatt T.K., Krivoshapkin P.V., Krivoshapkina E.F.

A third of food produced for human consumption is wasted on the way from the farm to the table. This is very evident in fruits and vegetables, perishable foods that are particularly susceptible to physical, chemical, and microbiological spoilage, resulting in poor appearance, smell, taste, and texture, as well as a shorter shelf life. This has prompted the exploration of different preservation techniques. One of the proposed methods is the use of biodegradable biocompatible silk-based food-friendly coatings with antimicrobial properties. Recently, several types of silk-based intelligent and active food packaging have also been proposed, proving that silk has many potential applications in the food industry. This review explores spider silk and silk fibroin as potential food coatings and smart packaging for prolonging fruit and vegetable freshness. Silk is a very versatile biomaterial that has piqued the interest of the food industry over the past two decades. This has led to the emergence of silk-based food coatings and smart packaging that ensure that consumers receive safe, high-quality food products. • Horticultural produce preservation. • Silk-based food coatings for food quality and safety control. • Intelligent and active silk-based food packaging.

Temnikova M., Medvedev J., Medvedeva X., Delva N.H., Khairullina E., Krivoshapkina E., Klinkova A.

AbstractUpgrading biomass‐derived compounds to value‐added products, especially fuels, represents a green route alternative to fossil fuels energy sources. Here, we report an efficient electrosynthesis of a jet fuel precursor hydrofuroin from furfural, which is one of the most valuable compounds derived from biomass. Despite the high value of this process, few studies have been focused on the development of synthetic strategies for electrocatalytic hydrodimerization of furfural to hydrofuroin. In this work, we systematically examine how operating parameters, including the electrolyte, applied potential, furfural concentration, and catalyst nature affect the efficiency of hydrofuroin electrosynthesis in organic media. We show that under the optimized conditions, the electrosynthesis can be carried out in a simple undivided cell with a high faradaic efficiency (up to 74 %) and an excellent hydrofuroin yield (up to 100 %).