Biomass-based Catalyst Research Articles

Remote Sulfonylation of Anilines with Sodium Sulfifinates Using Biomass-Derived Copper Catalyst

A biomass-based catalyst, CuxOy@CS-400, was employed as an excellent recyclable heterogeneous catalyst to realize the sulfonylation reaction of aniline derivatives with sodium sulfinates. Various substrates were compatible, giving the desired products moderate to good yields at room temperature. In addition, this heterogeneous copper catalyst was also easy to recover and was recyclable up to five times without considerably deteriorating in catalytic efficiency. Importantly, these sulfonylation products were readily converted to the corresponding 4-sulfonyl anilines via a hydrolysis step. The method offers a unique strategy for synthesizing arylsulfones and has the potential to create new possibilities for developing heterogeneous copper-catalyzed C-H functionalizations.

Biomass carbon with defective structures as effective ORR catalyst for DMFC

Oxygen reduction reaction (ORR), as an important reaction carried out on the cathode of direct methanol fuel cells (DMFC), directly affects the performance of the cell. Previous experimental studies have shown that there are some interactions between the defect structure and N doping to promote the ORR performance of the catalysts. In this work, the binder was first utilized to reduce the lignin content in the cotton straw (CS) system, thereby increasing the defective structure of the carbon substrate. Here, we obtained 5C-NP-Fe catalysts by increasing the defectivity of the carbon substrate through binder. The coordination environment surrounding the Fe-N4 sites is optimized by the synergistic action of the N and P atoms and the faulty structure, as shown by DFT theoretical calculations. In alkaline medium, half-wave potentials as high as 0.88 V in the three-electrode system and a peak power density of 10.8 mW cm−2 in a direct methanol fuel cell at 60℃. Compared to a 20 wt% commercial Pt/C catalyst (0.84 V, 7.5 mW cm−2), 5C-NP-Fe showed good ORR activity. The binder modification strategy provides a simple and green approach to the structural optimization of biomass-based catalysts.

Plasma Modification of Biomass-Based Starfish Catalysts for Efficient Biodiesel Synthesis.

This study investigated biodiesel production via the transesterification of grapeseed oil with plasma-modified biomass-based catalysts originating from starfish. Dried starfish was first converted into magnesium and calcium oxide through heat treatment and then further modified by plasma engineering to improve the catalyst's surface area and active sites via zinc addition. The Zn content was added via plasma engineering in the ratios of starfish (Mg0.1Ca0.9CO3): ZnO varying from 5:1, 10:1, to 20:1. The structure and morphology of the catalyst were confirmed through XRD, SEM, and XPS analysis. After the Zn addition and activation process, the surface area and the basicity of the synthesized catalysts were increased. The plasma-modified catalyst showed the highest basicity at the ratio of 10:1. Based on HPLC analyses, the optimized biodiesel yield in transesterification demonstrated 97.7% in fatty acid conversion, and its catalytic performance maintained 93.2% even after three repeated runs.

Development of hydrogen peroxide based micro thruster utilizing biomass-based catalyst bed

Micro thrusters, also referred to as micro-newton thrusters, are thrusters having a wide range of force capabilities in the micro-newton range. Micro thrusters are used in CubeSats, tiny robots and drones, micro- and nanosatellites, spacecraft attitude control, etc. The aim of the present study is to develop a monopropellant thruster (MPT) for 90 % concentrated hydrogen peroxide (H2O2). A rotatory evaporator was used to obtain a 90 % H2O2 form the available concentration of 50 % H2O2. The next stage involved the designing of the monopropellant thruster utilizing the NASA CEA rocket performance algorithm and the derived mathematical model. The test facility was constructed which includes a thruster, a feed line system, a static test firing platform, a data collecting system and the measuring sensors. To measure the thrust of the thruster, a pendulum thrust mechanism was constructed and fabricated into an experimental test stand. Lastly, the MPT chamber, which uses stainless steel mesh, was prepared and packed with the biomass-based catalyst. The 14 bar injection pressure conditions were used for the fire tests. With a mass flow rate of 5 g/s and a decomposition pressure of 10 bar, the theoretical specific impulse (Isp) was calculated to be 1993.2 Ns/kg at an O/F ratio of 0.002. The test firing with 90 % concentrated hydrogen peroxide gave an experimental specific impulse of 794.5 Ns/kg, which gives efficiency of 39.9 %.

Lignin-tailored fabrication of Ni single atom catalyst with Ni-N3 active site for efficient and selective catalytic transfer hydrogenation of lignin-derived aldehydes

Developing sustainable catalytic processes for catalytic transfer hydrogenation (CTHDO) of lignin-derived aldehydes to renewable fuels and chemicals is essential for scale valorization of vast underused lignin. Herein, the work contributes to the efficient and selective vanillin (VAN) CTHDO process using formic acid (FA) as the H-donor over a novel lignin-coordinated N-anchoring Ni single-atom catalyst (Ni SAs-N@LC). Ni SAs-N@LC was fabricated through facile pyrolysis of lignin-Ni/Zn complex mixed with melamine, in which lignin localized the Ni atoms through its negatively charged groups (e.g. phenolic OH) and the dispersed Ni atoms were further anchored by the N-doped carbon support to form Ni-N3 active structure. DFT calculations revealed that the Ni-N3 structure preferentially adsorbed the –CHO end of VAN and endowed the catalyst with superior hydrogen evolution capacity. Therefore, Ni SAs-N@LC exhibited outstanding catalytic performance (98.93% of VAN conversion and 97.3% of 2-methoxy-4-methylphenol selectivity) which was significantly higher than two reference catalysts Ni NPs@LC (without N-anchoring) and Ni@C (without lignin coordination and N-anchoring) as well as the previously reported Ni-based catalysts. Moreover, Ni SAs-N@LC presented excellent feasibility to the CTHDO of a wide range of lignin-derived aldehydes and exhibited superior cycling durability in FA system owing to its acid resistance property. Consequently, this work provides a facile preparation method for atomically dispersed biomass-based catalysts and further demonstrates its favorable applicability in the CTHDO of lignin-derived aldehydes.

High-density Co-Nx sites anchored on biomass-based carbon nanotubes for efficient removal of plant viruses in water

In this study, we selected rice straw, wheat straw and corn cob as raw materials to successfully prepare cobalt-nitrogen co-doped biomass-based carbon nanotubes composites (BM@CoNCNTs) with Co-Nx sites highly dispersed on porous biochar carrier, which could effectively activate peroxymonosulfate (PMS) to remove tobacco mosaic virus (TMV) in water. Particularly, BM@CoNCNTs-CC, with its confined carbon nanotubes and high-density Co-Nx sites, enhanced the Co2+/Co3+ cycle and direct adsorption of PMS to generate Co(IV)=O and 1O2, playing a dominant role. This led to the effective disruption of TMV coat protein and degradation of its genome within 5 min, achieving up to 6 log10 removal efficiency. Additionally, BM@CoNCNTs-CC/PMS system maintained efficient catalytic removal performance even in complex water matrices (river water and tap water). Overall, our research not only elucidates the production of efficient biomass-based catalysts for environmental remediation, but also highlights the application potential of biomass-based carbon nanotubes composites enriched with Co-Nx sites.

Production and testing of mahua oil-based biodiesel synthesized through heterogeneous catalyst using experimental and numerical method.

A two-step treatment of mahua oil was conducted to synthesize mahua biodiesel using heterogeneous biomass-based catalyst derived from mahua shell. Mahua oil having higher free fatty acid (FFA) content (about 19%) was esterified to reduce the FFA content up to 1%. The esterification process was carried out using 200mL mahua oil, 5:1 molar ratio (methanol:oil), and 2.25 weight% of H2SO4 at a temperature of 60°C for 3h. Post esterification, a set of 16 experiments were created using a Box-Behnken design (BBD)-based response surface methodology (RSM) approach to conduct the transesterification of the esterified oil. Molar ratio, catalyst loading, reaction temperature, and reaction time were the four input variables chosen for the design of experiments. The optimized conditions for maximum biodiesel yield (87.7%) were found to be 14.88 molar ratio, 3.578% catalyst loading, 69.7°C reaction temperature, and 81.9min reaction time. The Diesel RK engine simulation tool which was experimentally validated for baseline diesel fuel was used for numerical simulation of mahua biodiesel. The performance, combustion, and emission behavior of mahua biodiesel analyzed using numerical simulation presented the sustainability of mahua biodiesel as an alternate fuel.

Biomass-based carbon aerogels with interconnected pores and controllable Zn–N sites for CO2 electroreduction

The rational design of renewable, highly active, and selective catalysts has always been the key to the practical application of CO2 electroreduction. In this study, biomass-based Zn/N doped carbon aerogels were fabricated for high-selectivity electrical reduction of CO2 to CO. After in situ Zn/N doping, carbon aerogels exhibited interconnected pores, high surface area, and exposed active sites, and their physicochemical properties are significantly affected by pyrolysis temperature. When the pyrolysis temperature increased to 950 °C, the number of surface active sites and pore structure parameters of carbon aerogels decreased significantly due to the escape of zinc and nitrogen. CAZN-850 exhibited the highest specific surface area of 1317.0 m2/g and abundant Zn–N sites, which results in its high activity and selectivity for electroreduction of CO2 to CO (FECO = 89 % at −1.0V vs. RHE). Moreover, the stability test results for CO2RR showed that the reduction value of FECO for Zn/N doped carbon aerogels was only 5 % under long-time operation. This work provides a new idea for the design of biomass-based catalysts for CO2 electroreduction.

Conversion of 5-hydroxymethylfurfural and carbohydrates to 5-ethoxymethylfurfural over chitin-derived solid acid catalysts

The use of environment friendly biomass-based catalysts in bio refinery is highly desirable. In this paper, the preparation of sulfonated carbon materials from biopolymers (typically chitin and cellulose) via facile one-step carbonization and sulfonation using p-toluenesulfonic acid as sulfonating agent was demonstrated. Unlike nitrogen-free cellulose, the basic nitrogen-containing sites generated from chitin decreased the acidity strength of the catalysts, which was confirmed by the results of 31P Nuclear Magnetic Resonance (31P NMR). The suppressed acidity strength boosted the selectivity of 5-ethoxymethylfurfural (EMF) from 5-hydroxymethylfurfural (HMF) by inhibiting the formation of by-products, such as ethyl levulinate (EL) and humins. An 84.3 % yield of EMF from HMF was obtained over the as-prepared chitin-derived solid acid. The catalyst could be reused at least three times without obvious decrease of catalytic activity. Moreover, 74.6 %, 31.9 % and 60.7 % yields of EMF were obtained from fructose, sucrose and inulin in ethanol-containing solvents, respectively. This work offers an example for the synthesis of biofuels using biomass-derived catalysts.

The potential of biochar derived from banana peel/Fe3O4/ZIF-67@K2CO3 as magnetic nanocatalyst for biodiesel production from waste cooking oils

Using biomass-based catalysts in biodiesel production can make the process more economical and environmentally friendly. In this study, a new magnetic nanocatalyst was developed using banana peel biochar, ZIF-67, Fe3O4, and K2CO3, and then utilized in a catalytic transesterification process to convert waste cooking oils (WCO) into biodiesel. The level of free fatty acids of the treated WCO (WCOT) was reduced to generate a biodiesel with more suitable characteristics. The physicochemical aspects of the magnetic nanocatalyst were characterized by Fourier-transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) and map techniques. In the transesterification process, the effect of temperature, methanol-to-oil ratio, process time, and nanocatalyst weight on the potential of nanocatalyst to produce biodiesel from WCO and WCOT was explored. The highest yield of biodiesel from WCO (96.82%) and WCOT (99.18%) was attained at 65 °C, nanocatalyst weight of 3 wt %, methanol-to-oil ratio of 19:1, a processing time of 3 h, and a mixing rate of 600 rpm. Based on thermodynamic studies, the biodiesel production process was endothermic and non-spontaneous. The regeneration of the nanocatalyst was studied using various solvents and n-hexane had a good ability to recover the catalyst (90% up to 5 stages). The results of the 1H NMR test revealed that the desired nanocatalyst had a high potential to generate biodiesel from WCO and WCOT. The properties of produced biodiesel met ASTM D6751 and EN 14214 standards.

Tea saponin-derived porous carbon bearing rich oxygen-containing groups towards high efficient CO2 fixation

The effective utilization of biomass resources can bring significantly environmental and economic benefits. In this context, tea saponin, which can be easily and extensively extracted from the oil cake as the biomass waste during the seed oil production from camellia seeds, is explored as the precursor to synthesize porous carbon bearing abundant –OH and –COOH groups via a simple carbonization process. Owing to the obtained porous structure and existence of rich oxygen-containing groups serving as Lewis acidic sites, the carbonized tea saponin (CTS) can display impressive catalytic activities for CO2 cycloaddition reaction with both high selectivity (> 99%) and high yield of target cyclic carbonate under either thermally driven (80 °C and 0.1 MPa CO2) or photo-thermally driven (UV-Vis light irradiation with the light intensity of 350 mW/cm2) conditions. In addition, benefiting from the good chemical stability, CTS can be reused for many cycles with almost no catalytic activity loss, making CTS a promising biomass-based catalyst for CO2 fixation under mild conditions.

Highly dispersed palladium nano-catalyst anchored on N-doped nanoporous carbon microspheres derived from chitosan for efficient and stable hydrogenation of quinoline

Under the background of green chemistry, the synthesis of N-heterocycles using efficient, stable and long-life catalysts has still faced great challenges. Herein, we used biomass resource chitosan to fabricate a nanoporous chitosan carbon microsphere (CCM), and successfully designed a stable and efficient Pd nano-catalyst (CCM/Pd). Various physicochemical characterizations provided convincible evidences that the palladium nanoparticles (NPs) were tightly and evenly dispersed on the CCM with a mean diameter of 2.28 nm based on the nanoporous structure and abundant functional N/O groups in CCM. Importantly, the graphitized constructure, the formed defects and larger surface area in CCM were able to promote the immobilization of Pd NPs and the electron transfer between Pd and CCM, thereby significantly improving the catalytic activity. The CCM/Pd catalyst was applied for hydrogenation of quinoline compounds, which showed excellent catalytic activity and durability, as well as good substrate applicability. The application of renewable biomass-based catalysts contributes to the progression of a green/sustainable society.

Catalytic Conversion of 5-Hydroxymethylfurfural and Fructose to 5-Ethoxymethylfurfural over Sulfonated Biochar Catalysts

5-Hydroxymethylfurfural (HMF) is a key platform compound that can be produced by the dehydration of typical carbohydrates like glucose and fructose. Among the derivatives of HMF, 5-ethoxymethylfurfural (EMF) is the etherification product of HMF with ethanol. Owing to some advantages (i.e., high energy density), EMF has been regarded as a potential liquid fuel. Therefore, catalytic conversion of HMF and fructose to EMF is of significance, especially using heterogeneous catalysts. In this paper, we demonstrated the preparation of biomass-based catalysts for the synthesis of EMF from HMF and fructose. Some sulfonated biochar catalysts were prepared by the carbonization of biomass-based precursors at high temperature in N2, followed by the subsequent sulfonation process employing concentered H2SO4 as sulfonation reagent. The obtained catalysts were characterized by scanning electron microscope (SEM), Fourier transform infrared spectrometer (FT-IR), X-ray diffraction (XRD), and element analysis. The catalytic conversion of HMF to EMF was carried out in ethanol, providing a 78% yield with complete conversion at 120 °C. The catalytic activity of the used catalyst showed slight decrease for the etherification of HMF. Moreover, the catalysts were effective for the direct conversion of fructose towards EMF in 64.9% yield. Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Investigation of the performance of metal-free catalyst prepared from black tea and green tea waste for hydrogen production via methanolysis of sodium borohydride and optimization using response surface methodology

This study uses a waste biomass-based (green tea leaves and black tea leaves) catalyst for hydrogen production by methanolysis of sodium borohydride (NaBH4) in two ways. The Response Surface Methodology was used for parameter optimization of HGR using AAPC-WGTL and AAPC-WBTL at various parameters such as amounts of catalysts, NaBH4, and reaction temperature. In the case of the AAPC - WBTL catalyst, the highest HGR of 7676 ml min−1 g catalyst−1 was observed at 0.25 g NaBH4, 0.1 g catalyst, and 10 ml methanol (CH3OH) at 50 °C. For the AAPC - WGTL catalyst, the highest HGR of 9084.75 ml min−1g catalyst−1 was observed at 0.15 g NaBH4, 0.1 g catalyst, and 10 ml CH3OH at 50 °C. Moreover, the activation energies were found to be 47.06 kJ/mol and 47.89 kJ/mol for the AAPC-WBTL and AAPC-WGTL catalysts, respectively. FTIR, BET, SEM-EDS, HRTEM and XPS characterized the catalyst. The BET analysis shows that AAPC – WGTL and AAPC-WBTL catalysts have surface areas of 22.96 m2/g and 3.28 m2/g, pore diameters of 1.72 nm and 1.70 nm and pore volumes of 0.0047 cm3/g and 0.0331785 cm3/g respectively. Furthermore, Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) were performed. The AAPC-WGTL and AAPC-WBTL electrode shows 121 mF/cm2 and 63.77 mF/cm2 capacitance, respectively. Therefore, it can be said that WGTL and WBTL are both biomass capable of producing H2 using methanolysis of NaBH4.

Coconut waste valorization to produce biochar catalyst and its application in cellulose-degrading enzymes production via SSF

Solid waste management and waste valorization are key concerns and challenges around the globe. Solid wastes generated by food industries are found in a diverse variety, are key sources of enormously valuable compounds, and can be effectively transformed into useful products for broad industrial applications. Biomass-based catalysts, industrial enzymes, and biofuels are some of the very prominent and sustainable products that are developed using these solid wastes. The aims of the current study are therefore centered on the multiple valorizations of coconut waste (CWs) to develop biochar as a catalyst and its application in fungal enzyme production in solid-state fermentation (SSF). Biochar as a catalyst using CWs has been prepared via a calcination process lasting 1 h at 500 °C and characterized through X-ray diffraction, Fourier-transformed infrared spectroscopy, and scanning electron microscope techniques. The produced biochar has been implemented for boosting enzyme production through SSF. In addition, studies have been performed on enzyme production with varying time and temperature, and it is found that the maximum 92 IU/gds BGL enzyme could be produced at a 2.5 mg concentration of biochar-catalyst at 40 °C in 72 h.

Design of a renewable catalyst support derived from biomass with optimized textural features for fischer tropsch synthesis

The feasibility of a renewable source for synthesis of mesoporous activated carbon (AC) as catalyst support in Fischer-Tropsch synthesis (FTS) has been investigated. For this purpose, machine learning was used to optimize the process conditions for synthesis of AC (through chemical activation) from biomass. Three different regression methods were carried out to optimize the activation time, temperature, and impregnation ratio. Random forest regression (RFR) resulted in the highest prediction accuracy with R2 of 0.88 and 0.97 for total pore volume (cm3/g) and mesoporosity (%), respectively. The prepared AC at optimum activation conditions (obtained by RFR) led to 90% mesoporosity. Prior to FT reaction, the mineral impurities of the AC were decreased using alkaline treatment. The performances of the Fe catalysts supported on AC (10Fe/AC and 20Fe/AC) were tested for FTS at 300 °C, 2 MPa, and gas hourly space velocity (GHSV) of 2000 h−1. The 20Fe/AC catalyst achieved 46.7% CO conversion and C5+ selectivity of 72.5%, indicating the promising potential of the biomass-based catalyst support with optimized textural features and modified surface for FTS. The 20Fe/AC catalyst showed superior FT activity and C5+ selectivity compared to the 20Fe/Al2O3, and Fe catalyst supported on commercial AC. For 20Fe/AC catalyst, liquid hydrocarbons in the range of C5–C50 were detected.

Sulphonated biomass-based catalyst for solketal synthesis by acetalization of glycerol – A byproduct of biodiesel production

Research on biomass-based catalyst is beneficial for the sustainability of biodiesel industry owing to its wide availability of feedstock, non-toxicity and biodegradability. Cellulose based heterogeneous solid carbon catalyst was prepared from cellulose by treating cellulose with concentrated sulphuric acid in innocuous hydrothermal conditions. It shows promising potential as a suitable catalyst for the synthesis of solketal (a biofuel additive) by acetalization of glycerol, the waste product of biodiesel production. 97.1 ± 0.4% of solketal was produced under the optimum conditions of 1:5 M ratio of glycerol and acetone, catalyst loading of 7 wt% at 70 °C in 10 min. 90% of catalytic activity was retained even after five catalytic cycles making the catalyst highly efficient. With further investments; this method may be used for the preparation of biofuel additive in an industrial level.

Recent Advances in the Valorization of Biodiesel By-Product Glycerol to Solketal

The exponential rise of the biodiesel production has resulted in a considerable amount of glycerol as a by-product, which must be valorized to ensure the sector’s long-term viability. As a result, cost-effective glycerol conversions for significant value-added chemicals are essential for the biodiesel production in the long run. Solketal, a glycerol by-product, is obtained as a potential fuel additive in the biodiesel industry. Recently, several heterogeneous acid-catalysts stand out as a promising catalyst for solketal production where biomass-based catalyst gained attraction owing to their biodegradability, eco-friendly, and abundant availability. Furthermore, magnetic nanoparticles-derived catalysts along with sulfonated functionalized catalyzed, zeolites, resins, enzymatic, etc. have proved their efficiency in solketal production. In this review, a wider study on the recent advances of the catalysts has been discussed along with their preparation, various reaction parameters, its application, and efficiency for biodiesel industry. This study opens up incredible prospects for us to use renewable energy sources, which will benefit the industry, the environment, and the economy.

A Highly Effective Biomass-Derived Solid Acid Catalyst for Biodiesel Synthesis Through Esterification.

Efficient valorization of renewable liquid biomass for biodiesel production using the desirable biomass-based catalysts is being deemed to be an environmentally friendly process. Herein, a highly active biomass-based solid acid catalyst (SiO2@Cs-SO3H) with renewable chitosan as raw material through sulfonation procedure under the relatively mild condition was successfully manufactured. The SiO2@Cs-SO3H catalyst was systematically characterized, especially with a large specific surface area (21.82 m2/g) and acidity (3.47 mmol/g). The catalytic activity of SiO2@Cs-SO3H was evaluated by esterification of oleic acid (OA) and methanol for biodiesel production. The best biodiesel yield was acquired by Response Surface Methodology (RSM). The optimized reaction conditions were temperature of 92°C, time of 4.1 h, catalyst dosage of 6.8 wt%, and methanol to OA molar ratio of 31.4, respectively. In this case, the optimal experimental biodiesel yield was found to be 98.2%, which was close to that of the predicted value of 98.4%, indicating the good reliability of RSM employed in this study. Furthermore, SiO2@Cs-SO3H also exhibited good reusability in terms of five consecutive recycles with 87.0% biodiesel yield. As such, SiO2@Cs-SO3H can be considered and used as a bio-based sustainable catalyst of high-efficiency for biodiesel production.

Valorization of Biomass to Furfural by Chestnut Shell-based Solid Acid in Methyl Isobutyl Ketone-Water-Sodium Chloride System.

Recently, highly efficient production of furfural from available, abundant, inexpensive, and renewable lignocellulosic biomass has gained much attention by using biomass-based heterogeneous catalyst in an effective biphasic system. Using microwave-treated chestnut shell (MC-CNS) as biobased support, biomass-based catalyst (MC-Sn-CNS) was firstly synthesized for catalyzing biomass into furfural. The structure parameters of MC-Sn-CNS were measured by BET, SEM, XRD, and FT-IR. After systematical optimization, furfural yield reached 64.4% from corncob by MC-Sn-CNS (3.6 wt%) at 180°C for 15min in methyl isobutyl ketone (MIBK)-water (2:1, v:v) containing 200mM NaCl. MC-Sn-CNS had high stability, which could be recycled for 7 batches. The yield of furfural from fresh corncob was 44.5-64.4%. The possible catalytic mechanism for synergistic catalysis of biomass to furfural by MC-Sn-CNS was expounded in MIBK-water-NaCl system. The results showed that green solvent (MIBK) and NaCl promoted the production of furfural from CC catalyzed by solid acid (MC-Sn-CNS). This study demonstrated an environmentally friendly strategy for efficiently utilizing corncob into furfural by CNS-based heterogeneous chemocatalyst in a green reaction media. Clearly, this newly synthesized biomass-based MC-Sn-CNS catalyst had potential application in the future.