Biochar Catalyst Research Articles

Synthesis of metal-free heteroatom (N, P, O, and B) doped biochar catalysts for enhanced catalytic co-pyrolysis of walnut shells and palm oil fatty acid distillate to produce high-quality bio-oil

In the current study, sugarcane bagasse-derived biochar catalysts were synthesized by doping with metal-free heteroatoms including nitrogen, phosphorus, oxygen, and boron and their efficacy was tested for catalytic co-pyrolysis of walnut shells (WS) and palm oil fatty acid distillate (PFAD) using Py-GC/MS. The biochar catalysts’ properties and their effectiveness on co-pyrolytic bio-oil (overall product distribution, selectivity towards aliphatic and aromatic hydrocarbons, and carbon number ranges) were extensively examined. Among the various catalysts considered, boron-doped biochar (BCB) demonstrated effective performance due to an improved surface area, porosity, and acidity and resulted in a significantly increased hydrocarbon yield, particularly in the gasoline and diesel range, and preference for aromatic over aliphatic hydrocarbons. The optimum bio-oil quality was achieved at a feedstock-to-catalyst ratio of 2:1 and a pyrolysis temperature of 750 °C, with a hydrocarbon yield of 90.8 % and aromatic hydrocarbon selectivity of 63.5 %. Overall, the study underscores the role of BCB in fostering deoxygenation, decarboxylation, and aromatic selectivity via thermal and catalytic pathways, highlighting the potential of non-metallic doped biochars for bio-oil upgrading.

Optimization of Photothermal Catalytic Reaction of Ethyl Acetate and NO Catalyzed by Biochar-Supported MnOx-TiO2 Catalysts.

The substitution of ethyl acetate for ammonia in NH3-SCR provides a novel strategy for the simultaneous removal of VOCs and NO. In this study, three distinct types of biochar were fabricated through pyrolysis at 700 °C. MnOx and TiO2 were sequentially loaded onto these biochar substrates via a hydrothermal process, yielding a family of biochar-based catalysts with optimized dosages. Upon exposure to xenon lamp irradiation at 240 °C, the biochar catalyst designated as 700-12-3GN, derived from Ginkgo shells, demonstrated the highest catalytic activity when contrasted with its counterparts prepared from moso bamboo and loofah. The conversion efficiencies for NO and ethyl acetate (EA) peaked at 73.66% and 62.09%, respectively, at a catalyst loading of 300 mg. The characterization results indicate that the 700-12-3GN catalyst exhibits superior activity, which can be attributed to the higher concentration of Mn4+ and Ti4+ species, along with its superior redox properties and suitable elemental distribution. Notably, the 700-12-3GN catalyst has the smallest specific surface area but the largest pore volume and average BJH pore size, indicating that the specific surface area is not the predominant factor affecting catalyst performance. Instead, pore volume and average BJH pore diameter appear to be the more influential parameters. This research provides a reference and prospect for the resource utilization of biochar and the development of photothermal co-catalytic ethyl acetate and NO at low cost.

High-efficient microwave-assisted conversion of fructose to 5-hydroxymethylfurfural over rice straw-derived sulfonated porous carbonaceous catalyst

5-Hydroxymethylfurfural (HMF) has emerged as a pivotal platform chemical derived from biomass, attracting considerable attention for its renewable applications. In this study, sulfonated rice straw biochar (RSBC-SA) catalysts were developed and employed for microwave-assisted catalytic conversion of fructose to HMF. The RSBC-SA catalysts, synthesized by pyrolyzing rice straw biomass at different temperatures and subsequent functionalization with sulfonic acid groups, were characterized using X-ray photoelectron spectroscopy (XPS), elemental analysis, temperature programmed desorption (TPD) and Fourier-transform infrared spectroscopy (FT-IR). A comparative analysis of catalytic performance between microwave irradiation and conventional oil bath heating revealed a substantial enhancement in efficiency with the former. Notably, the 700 ℃ pyrolyzed RSBC-SA catalyst demonstrated the highest HMF yield of 92.6 % within just 5 min of reaction time under a microwavehydrothermal condition, surpassing the conventional oil bath heating method. In addition, moderate to high yields of HMF were achieved from different carbohydrates in our developed microwave reaction system, demonstrating significant catalytic activity. This superior catalytic effect under microwave irradiation can be attributed to the responsive dipole polarization of sulfonic acid groups, selective heating of the RSBC carrier via microwave absorption, and synergistic interactions among these factors. Overall, this study highlights the innovative use of agricultural waste and introduces a new method for creating microwave-responsive catalysts with biochar. This strategy enables efficient fructose conversion to HMF, promotes sustainable biomass transformation, and offers value-added uses for agricultural residues in chemical production.

Pyrolysis and catalytic upgrading of pine wood sawdust over modified biochar catalyst in a tandem microreactor

A series of novel catalysts were prepared by modifying biochar (BC) with different metal loading (Fe, Zn) and thermal activation in different atmospheres (CO2, H2O). The catalysts were further used to upgrade the pyrolysis vapor from pine wood sawdust, aiming to produce high-quality bio-oil. The modified biochar catalyst exhibited strong deoxygenation ability to acids and ketones in bio-oil and effectively converted lignin-derived compounds into aromatic hydrocarbons and phenols. Subsequently, the catalyst (BC-Fe-CO2) demonstrating the highest yields of phenols and aromatics was selected for condition optimization. Different catalytic temperatures and biomass-to-catalyst ratios were compared to determine the optimal conditions for producing high-quality bio-oil. Phenolics and aromatic hydrocarbons content in the bio-oil reached 70 % at the optimal condition and the selectivity of monocyclic aromatic hydrocarbons in aromatic hydrocarbons reached 77 %. The properties of the biochar catalysts were characterized using BET, SEM, XRD, and XPS. The superior performance of the modified BC catalysts not only relied on its enhanced surface area and porous structure but also due to active Fe sites. The detail reaction pathways of the bio-oil catalytic upgrading were also proposed. These findings underscore the potential of modified biochar in pyrolysis and catalytic upgrading for bio-oil with improved quality.

Agro-waste derived sulfonated biochar material as a sustainable heterogeneous catalyst for conversion of fructose to 5-hydroxymethylfurfural

BackgroundDevelopment of biomass derived solid acid catalysts has the advantage to conform the green chemistry protocol for production of 5-hydroxymethylfurfural (HMF) by dehydration of fructose. MethodWe have reported waste cashew nut shell produced char as a biochar to prepare sulfonated biochar (SBC) catalyst by incorporating –SO3H group through treatment of concentrated sulfuric acid. Significant findingsDifferent methods of characterization including XRD, FT-IR, XPS, FESEM-EDS, TEM, TPD and BET analysis, were used to study the structure, morphology, chemical compositions, acidity and porosity of the produced SBC catalysts. The mesoporous nature of the material was confirmed by the powder X-ray diffraction patterns (PXRD), type IV isotherm (BET), and flakes-like structure was observed in TEM analysis. The catalyst showed high yield of HMF (92%) under optimum conditions of 120 °C in 60 min under biphasic solvent mixture of water and toluene (1:2). High yield could be explained by high acid strength of catalyst as observed by NH3-TPD analysis. Leaching test by Sheldon's method and recyclability experiment proved the need and heterogeneity of the present catalyst.

Investigation of products characteristics from microwave catalytic pyrolysis of furfural residue based on the effects of Fe/Mn modified biochar

In this paper, the effect of MnCl2 and FeCl3 modified biochar catalysts on the catalytic pyrolysis products of furfural residue (FR) under microwave field was investigated. The results showed that the highest content in the pyrolysis gas obtained from microwave catalytic pyrolysis (MCP) with modified biochar catalysts was CO, while phenols were found in bio-oil. After metal loading, the specific surface area of the catalyst decreased significantly. The CO production was promoted by microwave pyrolysis of FR over modified biochar catalyst, and MFRC gain was more obvious. The content of H2 all continued to increase with increasing mass of loaded metals, and the opposite was true for CO. The highest relative content of phenols in the bio-oils of FFRC and MFRC were 66.76 % for 2FFRC and 63.66 % for 4MFRC, where the relative content of phenols was 15.50 % and 19.27 %, respectively. The production of sugars and ketones was also promoted by Fe and Mn. The lower loading of active metals significantly promoted the conversion of pyrolysis vapors to phenols while releasing more CO. A possible mechanism of MCP of FR was proposed. The results showed that Fe/Mn-modified char-based catalysts could effectively modulate the composition of bio-oil.

Efficient activation of persulfate for tetracycline hydrochloride degradation by biochar prepared from corn stover doped with organic phosphorus sources

Proposed to prepare phosphorus-doped biochar catalyst materials by impregnation pyrolysis method using corn stover and different phosphorus source precursors as raw materials, and the batch-wise research revealed that the phosphorus source precursor, the doping ratio, and the pyrolysis temperature had a significant influence on the biochar properties. The biochar material Pb-C-4–600 prepared with (C4H9)3PO4 as phosphorus source precursor, 1:4 doping ratio, and pyrolysis temperature of 600 ℃ had an ID/IG = 0.914, pore size of 4.91 nm, and specific surface area of 173.9845 m²/g, which was 93.4 times higher than that of the pure biochar. The removal rate of TCH reached 99.77 % in 30 min under the reaction conditions of PMS concentration of 2 g/L, Pb-C-4–600 dosage of 1 g/L, and pH 3. Comparing the efficacy of Pb-C-4–600 and different catalysts for the degradation of TCH by activated PMS under the same reaction conditions, the degradation reaction rate of Pb-C-4–600 was 0.17663 min−1, which was 1.48 times higher than that of N-bio, 1.67 times higher than that of S-bio, and 2.64 times higher than that of B-bio, which further demonstrating the advantages of Pb-C-4–600 in similar composites. The oxidative degradation performance of other typical organic pollutants (BPA, phenol, AO7) was also good. The prominent reactive oxidizing radical in the system of Pb-C-4–600/PMS was SO4·−, and the system could adapt to a wide pH range.

Synthesis of N-doped porous biochar from chemical pollutant for efficient sulfadiazine degradation: Performance, mechanism and bio-toxicity assessment

Turning chemical wastes into valuable materials presently is a key challenge. Therefore, a facile method was employed upon synthesis of an N-doped porous biochar (NPBC) catalyst via pyrolysis of chemical pollutant (reactive red 2, RR2), urea, and NaHCO3. Using NaHCO3 activation, the NPBC/PMS system exhibited excellent catalytic efficiency for sulfadiazine (SDZ) degradation, which was attributed to the porous structure with abundant active species of graphitic C/N, C=O, –COOH, and C–S–C. Significantly, the NPBC displayed excellent environmental suitability, catalytic universality for the decomposition of common organic pollutants (i.e. bisphenol A, ciprofloxacin, tetracycline, and sulfamethoxazole) and catalytic recycling stability. In addition, free radical quenching and mechanism inspection demonstrated that 1O2 is the dominating reactive oxygen species (ROS) in the NPBC/PMS system. The most probable degradation pathway and mechanism are proposed. Finally, the biotoxicity of SDZ before and after degradation was evaluated by ECOSAR analysis and the germination tests of wheat seeds. This study not only provides a rational method for the facile synthesis of valuable materials from chemical pollutants, but also presents a direction for discovering metal-free catalysts with remarkable activity for water decontamination in the future.

Superhydrophobic biochars as catalysts for efficient hydrogen transfer in N-heterocycles and nitrobenzene reactions

The heteroatom-doped carbon nanomaterials can be the active catalysts in hydrogen transfer reactions, however, carbon-catalyzed hydrogen transfer processes in the absence of additives and cocatalysts have been rarely described. Herein, functional biochar catalysts (FBCs) were successfully fabricated from wheat straw by a simple scalable two-step strategy via reconstructing the catalytic active sites in carbon precursors and subsequently controlled carbonization. The characterization of FBCs was discussed with regard to morphologic structures, chemical constitutions and performance, revealing that the high hydrophobicity is beneficial for obtaining high activity. Wherein the optimized FBC-850 catalyst exhibited high activity and durability toward the reaction of N-heterocycles and nitrobenzene in the aqueous systems due to the synergistic effects that were attributed to the external superhydrophobicity, internal capillary repulsion and hydrogen transfer property, eliminating the need for additional co-catalysts or additives. In the model reaction, the yields of quinoline and aniline were respectively achieved at 92% and 90%. Furthermore, the encapsulated quinone units as the active sites in FBC-850 formed the bipyramidal structure, enabling the hydrogen transfer process through a cyclical hydrogen exchange, which was proved from kinetic studies combined with spectral characterization and theoretical calculation. In addition, a possible reaction mechanism was proposed based on the observation of key intermediates and DFT calculations, also providing a rationale for the existing active site structures.

Synergistic activation of peroxymonosulfate by 3D CoNiO2/Co core-shell structure biochar catalyst for sulfamethoxazole degradation

In this study, a 3D CoNiO2/Co core–shell structure biochar catalyst derived from walnut shell was synthesized by hydrothermal and ion etching methods. The prepared BC@CoNi-600 catalyst exhibited exceptional peroxymonosulfate (PMS) activation. The system achieved 100 % degradation of sulfamethoxazole (SMX). The reactive oxygen species in the BC@CoNi-600/PMS system included SO4−, OH, and O2−. Density functional theory calculations explored the synergistic effects between nickel–cobalt bimetallic and carbon matrix during PMS activation. The unique 3D core–shell structure of BC@CoNi-600 features an outer nickel–cobalt bimetallic layer with exceptional PMS adsorption capacity, while protecting the zero-valence Co of the inner layer from oxidation. Based on the experimental-data, machine learning modeling mechanism, and information theory, a nonlinear modeling method was proposed. This study utilizes a machine learning approach to investigate the degradation of SMX in complex aquatic environments. This study synthesized a novel biochar-based catalyst for activated PMS and provided unique insights into its environmental applications.

Exploring electron-transfer pathways in co-pyrolyzed waste-derived carbocatalyst for enhanced peroxydisulfate activation

Heterogeneous catalyst-activated peroxydisulfate (PDS) process has great potential in environmental remediation, but its complex preparation process, high cost, low efficiency, and unclear mechanism hinder its practical application. To overcome these limitations, we introduced an innovative metal-free biochar catalyst (SCSS-NC) derived from waste biomass through co-pyrolysis of shrimp shell and sludge with nitrogen doping. This catalyst improved its performance, achieving 78.45 % degradation of tetracycline, outperforming sludge carbon/PDS systems (46.89 %) and shell carbon/PDS systems (22 %) under the dosage of PDS (0.5 mM) and catalysts (0.5 g/L) within 60 min. This improvement stems from its increased surface area, porosity, and electron transport capabilities. Quenching experiments, delayed contaminant addition experiments, and EPR results demonstrated that the SCSS-NC/PDS system relies on electron transfer, in which activated PDS binds to the catalyst surface, forming a highly reactive composite [SCSS-NC/PDS]* to degrade pollutants. The open-circuit potential and linear scanning voltammetry results confirm the existence of an electron transfer pathway, while the situ Raman spectroscopy results validate the presence of the composite [SCSS-NC/PDS]*. The DFT theoretical calculations provide further confirmation of the conductivity, low energy barrier, and ability to expedite electron transfer exhibited by SCSS-NC. The catalyst performance and characterization before, after, and post-recovery from the reaction pinpoint key active sites: pore adsorption, sp2 graphitic carbon, and graphitic nitrogen doping sites. The SCSS-NC/PDS system demonstrates robust anti-interference capability, suggesting its potential for practical organic wastewater treatment. This study provides novel insights into economical carbocatalyst and their mechanisms for environmental applications.

Efficient Preparation of Biodiesel Using Sulfonated Camellia oleifera Shell Biochar as a Catalyst.

This study prepared sulfonated Camellia oleifera shell biochar using Camellia oleifera shell agricultural waste as a carbon source, and evaluated its performance as a catalyst for preparing biodiesel. The biochar obtained from carbonizing Camellia oleifera shells at 500 °C for 2 h serves as the carbon skeleton, and then the biochar is sulfonated with chlorosulfonic acid. The sulfonic acid groups are mainly grafted onto the surface of Camellia oleifera shell biochar through covalent bonding to obtain sulfonic acid type biochar catalysts. The catalysts were characterized by Scanning Electron Microscope (SEM), X-ray diffraction (XRD), Nitrogen adsorption-desorption Brunel-Emmett-Taylor Theory (BET), and Fourier-transform infrared spectroscopy (FT-IR). The acid density of the sulfonated Camellia oleifera fruit shell biochar catalyst is 2.86 mmol/g, and the specific surface area is 2.67 m2/g, indicating high catalytic activity. The optimal reaction conditions are 4 wt% catalyst with a 6:1 alcohol to oil ratio. After esterification at 70 °C for 2 h, the yield of biodiesel was 91.4%. Under the optimal reaction conditions, after four repeated uses of the catalyst, the yield of biodiesel still reached 90%. Therefore, sulfonated Camellia oleifera shell biochar is a low-cost, green, non-homogeneous catalyst with great potential for biodiesel production by esterification reaction in future development.

Azadirachta indica leaf extract-derived NiS@Functionalized biochar catalyst: Efficient acetalization and enhanced reusability in photodegradation of tinidazole

Growing biodiesel production creates a significant volume of glycerol (Gly), a by-product that must be transformed into valuable compounds by developing novel and sustainable technologies. Solketal is one of several valuable compounds derived from residual Gly released during biodiesel synthesis. A green synthetic process followed by the co-precipitation method was used to fabricate NiS@Functionalized Biochar (NBS) using Azadrichta indica leaf extract. The nanocatalyst was extremely active for microwave-assisted solketal synthesis from Gly and acetone. A 99.7 ± 0.3 % conversion of Gly with 100 % solketal selectivity occurred under the optimum reaction conditions (catalyst loading 4 wt%, Gly to acetone molar ratio 1: 5, reaction time 6 min, and temperature 65 °C). The suggested reaction mechanism demonstrates the selective synthesis of solketal. The NBS catalyst showed excellent reusability up to six cycles, and after that, it was used for the photodegradation of tinidazole, where 89.14 % degradation efficiency was obtained within 110 min of sunlight irradiation. A narrow energy band gap (1.99 eV) and effective charge separation favor the photocatalytic activity of the reused catalyst. The environmental friendliness of the catalyst for the solketal synthesis process was examined by studying green metrics.

Catalytic oxidation of SO2 in O2-aerated aqueous Solution: superior catalytic capability of KOH/urea-treated biochars and catalytic mechanism

The catalytic oxidation of SO2 (COS) by dissolved oxygen in aqueous solution allows to recycle sulfate salt/sulfuric acid from the SO2-containing flue gas, and high-performance catalysts are desired for an efficient COS process. In this study, the chestnut leaves-derived biochars treated by the co-pyrolysis process with KOH/urea exhibited a favorable capability to catalyze the oxidation of SO2 in aqueous solution. The BK-N-8 biochar catalyst was the optimal one due to its moderate nitrogen content and appropriate surface functional groups. It exhibited a fast initial conversion rate from SO2 to SO42− (6.50 μmol g−1 s−1), and an excellent cycling durability for the COS process. The material showed a catalytic activity that surpassed all the reported carbonaceous materials. The surface functionalities were revealed to be the decisive factor for the conversion rate and durability of catalytic capacity. The superiority of the BK-N-8 with pyridinic N-doped aromatic cluster (AC) was further investigated via density-functional-theory calculations. The epoxy groups from O2 dissociation at the edge sites of ACs played a pivotal role for COS process onto biochars. This study provides insightful information for an in-depth understanding of the mechanism of COS process catalyzed by carbonaceous materials.

Synthesis of surficial-modified green biochar catalyst generated by biogas residue biochar and potential application for catalytic ozonation degradation of ciprofloxacin

This study synthesized novel, green, and easily recoverable surface-modified economical catalysts via hydrothermal treatment (HT) successfully, utilizing biogas residue biochar (BRB), a food waste product from anaerobic fermentation, pyrolyzed at 500 °C for 50 min. Using autoclaves, a total of six solutions were prepared, each having 1 g fine-grinded BRB, surficial modified by adding glycerol (GL) (10 or 20 mL) and SDI water (70 or 60 mL), and heated in an oven at 240 °C, 180 °C, and 120 °C for 24 h. Afterward, the catalysts showed the potential for degradation of widely used emerging pollutants like ciprofloxacin. Taking advantage of catalytic surface modification, the catalytic ozonation degradation was more effective than that of a single ozonation. However, under similar conditions, catalyst amount 0.20 g, ozone dose 15 mg L−1, and ciprofloxacin 80 mg L−1, the performance of the 10 mL GL-180 °C catalyst was excellent. It showed a 92.45%–94.41% optimum removal rate in the 8–10 min interval. After five continuous cycles, the 10 mL GL-180 °C catalyst exhibited excellent stability and reusability. XPS, FT-IR, BET, XRD, and SEM before and after the reaction confirmed the successful synthesis and degradation mechanism. A possible degradation pathway was unrevealed based on a liquid chromatography-mass spectrometer (LC-MS) and scavenger test, proving the significant roles of superoxide radicals (O2•-), hydroxyl radicals (•OH), and singlet oxygen (1O2). Further, Electron paramagnetic resonance (EPR) analysis confirmed the presence of active oxygen species. Subsequently, 10 mL GL-180 °C showed promising degradation for the actual water environment, such as groundwater (73.55%) and river water (64.74%). This work provides a valuable economic strategy to convert biogas residue biochar into a low-cost catalyst for organic pollutant decomposition.

Transesterification of used cooking oil by palm lignocellulosic biomass magnetic biochar catalyst: Optimization and kinetic analysis

Biodiesel has recently gained popularity as an alternative biofuel to substitute fossil fuel. Utilization of magnetic biochar catalyst (MBC) in biodiesel production can enhance the catalyst separation process. In this research, MBC was synthesized from oil palm waste such as palm kernel shell (PKS), oil palm frond (OFP), and empty fruit bunch (EFB). Biodiesel production parameters were studied using the Central Composite Design-based Response Surface Method. Based on the characterization results, EFB is the most suitable palm lignocellulosic biomass for MBC synthesis. The MBC has a BET surface area of 44.42 m2 g−1, an average acid density value of 3.85 mmol g−1, and a σs value of 3.19 Am2 kg−1. MBC synthesis is at its optimal by using 1.5 M FeCl3·6H2O solution, 800 °C carbonization temperature, and 2.5 M H2SO4. The optimized transesterification parameters are: catalyst loading of 10.25 wt%, methanol to oil molar ratio of 28, 70 °C, and 8 h gave a maximum fatty acid methyl ester yield of 91.50 %. After five cycles, the yield dropped to 67.37 %. Biodiesel production is reported to be the pseudo-irreversible first-order kinetic with an activation energy of 29.20 kJ mol−1. The physicochemical characterization showed the biodiesel has met the ASTM D6751 standard.

The activation of PMS for PFOA degradation by adjustable metal stripping Fe/Co/N@BC catalysts: Degradation performance with single-line oxygen and high-valent metal oxides as the main active substances

In this study, a modified biochar (P-Fe/Co/N@BC) catalyst was prepared with wood chips as raw material by hydrothermal method for the activation of peroxymonosulfate (PMS) and degradation of perfluorooctanoic acid (PFOA). Scanning electron microscopy (SEM), x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) characterization methods were used to demonstrate the presence of FeNx, CoNx, Fe-Co and CO active sites, which contribute to the improvement of the PMS activation capacity for single-line oxygen (1O2). Electron paramagnetic resonance spectroscopy (EPR), reactive oxygen species (ROS) scavenging experiments and methyl phenyl sulfoxide (PMSO) conversion experiments were performed to clarify the main mechanisms of PFOA degradation by reactive species. Further, 1O2, sulfate radical (SO4−), hydroxyl radical (OH), high-valent metal oxides (Fe(IV) and Co(IV)) were jointly involved in the degradation of PFOA, and nonradical were the main activation pathway of PMS. In particular, Fe3+ decomposed from Fe(IV) in the presence of Fe0 and Co2+ decomposed from Co(IV) are able to enhance iron cycling and cobalt cycling, respectively. Meanwhile, Co0 accelerates the conversion of Co3+ to Co2+. The findings suggested that the removal rate of the P-Fe/Co/N@BC-PMS system (99 %) was much higher than that of the P-Fe-N-C/PMS (68.9 %) over 180 min. It emphasized that the incorporation of PTFE (polytetrafluoroethylene) can regulate metal leaching significantly and improve the cycling stability of the catalysts. This study aimed to prepare efficient and stable modified biochar catalysts to activate PMS, which provided an effective solution to the problem of metal ion leaching from metal-modified biochar materials.

In situ N-doping engineered biochar catalysts for oxidation degradation of sulfadiazine via nonradical pathways: Singlet oxygen and electron transfer

Understanding the structure of non-metallic heteroatom-doped carbon catalysts and the subsequent degradation of new pollutants is crucial for designing more efficient carbon catalysts. Environmentally friendly in situ N-doped biochar catalysts were prepared for peroxymonosulfate (PMS) activation and sulfadiazine (SDZ) degradation. The acid washing process and calcination temperature of catalyst increased π-π* shake up, graphitic N percentage, specific surface area and defects, promoting the transformation of pollutant degradation mechanism from radical pathway to non-radical pathway. 100 % of the SDZ with the initial concentration of 10 mg/L was quickly degraded within 60 min using 0.2 g/L catalysts and 0.5 mM PMS. Excellent catalytic performance was attributed to singlet oxygen and electron transfer-dominated non-radical pathways. The four potential degradation pathways of SDZ were proposed, and toxicity predication indicated that overall biotoxicity of the intermediates during SDZ degradation was decreased. This research deepens our understanding of the mechanisms of non-radical pathways and guides the synthesis of carbon-based catalysts.

Enhancing the conversion of waste motor oil into diesel-like fuels using mineral-impregnated biochar catalysts

This study shows how the presence of metal-impregnated biochar influences the kinetics of the catalytic conversion of waste motor oil (WMO) into a diesel-like fuel (DLF). First, the initial metal concentration in the wet impregnation process was optimized, showing that high metal concentrations tend to clog the biochar pores, reducing the reaction’s conversion and speed. Zinc and calcium showed higher kinetic constants at the optimized conditions than nickel, while the yield- and selectivity-to-liquid products were unaffected. Then, a reduction method was developed for impregnating metal particles of calcium oxide to enhance the metal dispersion at the biochar surface. This material showed the best performance in the reaction due to the presence of small particles instead of metal agglomerates. An increase of about 280% in the kinetic constant at 420 °C and a much lower activation energy (246 kJ mol−1) compared to the thermal cracking (308 kJ mol−1) was obtained. Finally, the DLF from the best catalytic system was analyzed. Interestingly, the fuel showed similar rheological properties to commercial diesel with a similar hydrocarbon distribution but with the presence of smaller hydrocarbon chains.

Visible-light-driven photocatalytic degradation of doxycycline using TiO2/g-C3N4/biochar catalyst

Abstract TiO2/g-C3N4/biochar (TCNBC) catalysts were prepared by the hydrolysis method for the photocatalytic degradation of doxycycline antibiotic (DC), with biochar obtained from the pyrolysis of Phragmites australis. The catalysts were examined using scanning electron microscope (SEM), transmission microscopy (TEM), energy dispersive x-ray spectrometer (EDX), x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), photoluminescence spectroscopy (PL), and ultraviolet-visible diffuse reflectance spectroscopy (UV–Vis DRS) and nitrogen adsorption/desorption. The photocatalytic activity results showed that the TCNBC catalyst exhibited higher catalytic activity than pure TiO2 or g-C3N4. Its peak catalytic activity, achieving a decomposition efficiency of 91.93% and a mineralization efficiency of 81.50%, can be attributed to the synergistic effect of biochar, TiO2, and g-C3N4. Even after four cycles of use, the catalyst still maintained relatively high activity for the degradation of DC. The photocatalytic degradation efficiency of TCNBC decreased from 91.93% to 86.30% after four recycling events.