Boron niride microflakes of 2-5 μm in diameter and greater than 40 μm in length with multilayer structure and highly crystalline nature are synthesized in two states of catalysts and dual role of nitrogen at 1100 °C. Most of the microflakes are flat, smooth and vertically aligned with a wall-like view from the top. Transmission electron microscopy shows overlapped layers of microflakes with an interlayer spacing of 0.34 nm. The h-BN components of the synthesized microflakes are verified from B 1s and N1 s peaks at 190. 7 and 397.9 eV. Raman shift at 1370 (cm(-1)) and sharp peaks in the XRD pattern further confirm the h-BN phase and crystalline nature of the synthesized microflakes. Microflakes of h-BN with the above characteristics are highly desirable for the development of a solid state neutron detector with higher detection efficiency.
The current demands of sustainable green methodologies have increased the use of enzymatic technology in industrial processes. Employment of enzyme as biocatalysts offers the benefits of mild reaction conditions, biodegradability and catalytic efficiency. The harsh conditions of industrial processes, however, increase propensity of enzyme destabilization, shortening their industrial lifespan. Consequently, the technology of enzyme immobilization provides an effective means to circumvent these concerns by enhancing enzyme catalytic properties and also simplify downstream processing and improve operational stability. There are several techniques used to immobilize the enzymes onto supports which range from reversible physical adsorption and ionic linkages, to the irreversible stable covalent bonds. Such techniques produce immobilized enzymes of varying stability due to changes in the surface microenvironment and degree of multipoint attachment. Hence, it is mandatory to obtain information about the structure of the enzyme protein following interaction with the support surface as well as interactions of the enzymes with other proteins. Characterization technologies at the nanoscale level to study enzymes immobilized on surfaces are crucial to obtain valuable qualitative and quantitative information, including morphological visualization of the immobilized enzymes. These technologies are pertinent to assess efficacy of an immobilization technique and development of future enzyme immobilization strategies.
The aim of this study is to identify the optimum thermal conversion of Chlorella vulgaris with neuro-evolutionary approach. A Progressive Depth Swarm-Evolution (PDSE) neuro-evolutionary approach is proposed to model the Thermogravimetric analysis (TGA) data of catalytic thermal degradation of Chlorella vulgaris. Results showed that the proposed method can generate predictions which are more accurate compared to other conventional approaches (>90% lower in Root Mean Square Error (RMSE) and Mean Bias Error (MBE)). In addition, Simulated Annealing is proposed to determine the optimal operating conditions for microalgae conversion from multiple trained ANN. The predicted optimum conditions were reaction temperature of 900.0 °C, heating rate of 5.0 °C/min with the presence of HZSM-5 zeolite catalyst to obtain 88.3% of Chlorella vulgaris conversion.
Palm oil mill effluent (POME) is a serious and expensive environmental problem in Malaysia. In this paper, CaFe2O4 is introduced as a novel photocatalyst for the degradation of POME under visible light irradiation. Two synthesis routes, auto-combustion and co-precipitation, and two calcination temperatures 550 °C and 700 °C were used to produce four CaFe2O4 catalysts AC550, AC700, CP550 and CP700. CP550 exhibited the greatest photocatalytic degradation at 56% chemical-oxygen-demand (COD) removal after 8 h of irradiation which dropped to 49% after three consecutive cycles indicating reasonable conversion and high recyclability. BET analysis indicated CP550 had the highest SBET (27.28 m2/g) and pore volume (0.077 cm3/g) which dropped precipitously for CP700 upon increasing the calcination temperature to an SBET of 9.73 m2/g and pore volume of 0.025 cm3/g due to annealing which created a smoother surface area as evidenced by the SEM images. UV-Vis DRS indicated CP550 had the highest band-gap (1.52 eV) which is likely due to the presence of a highly crystalline pure CaFe2O4 phase compared to the other products which existed as a mixture of Fe oxidation states evidenced by the XRD data. The PL spectra for all catalysts indicated significantly lower recombination rate for both CP550 and CP700. Introduction of IPA into the reaction mixture to eliminate hydroxyl radicals resulted in a diminishing of COD removal from 56% to 7% proving hydroxyl radicals to be the primary reactive species responsible for photodegradation of POME.
Zeolite socony mobil-5 (ZSM-5) is a common catalyst used for biomass pyrolysis. Nevertheless, the quantitative information on the catalytic behavior of ZSM-5 on biomass pyrolysis is absent so far. This study focuses on the catalytic pyrolysis phenomena and mechanisms of biomass wastes using ZSM-5 via thermogravimetric analyzer and pyrolysis-gas chromatography/mass spectrometry, with particular emphasis on catalytic level identification and aromatic hydrocarbons (AHs) formation. Two biomass wastes of sawdust and sorghum distillery residue (SDR) are investigated, while four biomass-to-catalyst ratios are considered. The analysis suggests that biomass waste pyrolysis processes can be divided into three zones, proceeding from a heat-transfer dominant zone (zone 1) to catalysis dominant zones (zones 2 and 3). The indicators of the intensity of difference (IOD), catalytic effective area, catalytic index (CI), and aromatic enhancement index are conducted to measure the catalytic effect of ZSM-5 on biomass waste pyrolysis and AHs formation. The maximum IOD occurs in zone 2, showing the highest intensity of the catalytic effect. The CI values of the two biomass wastes increase with increasing the biomass-to-catalyst ratio. However, there exists a threshold for sawdust pyrolysis, indicating a limit for the catalytic effect on sawdust. The higher the catalyst addition, the higher the AHs proportion in the vapor stream. When the biomass-to-catalyst ratio is 1/10, AHs formation is intensified significantly, especially for sawdust. Overall, the indexes conducted in the present study can provide useful measures to identify the catalytic pyrolysis dynamics and levels.
Tetracycline (TC), a popularly found drug pollutant, can be contaminated in food and aquatic regions and causes a severe impact on human health. In this research, a visible light active p-stannic oxide/n-copper manganate (p-SnO2/n-CuMnO2) heterojunction was synthesized and has been applied for a signal on photoelectrochemical sensing of antibiotic TC. Firstly, the n-SnO2 microrods were synthesized via a simple and efficient homogeneous precipitation method and the p-CuMnO2 nanoparticles were synthesized by a facile ultrasound-assisted hydrothermal method. The SnO2/CuMnO2 microrods p-n heterojunction was prepared through a simple impregnation method and physicochemical properties of the microrods are characterized by using X-ray diffraction (XRD), Raman, Brunauer-Emmett-Teller (BET), Fourier-transform infrared (FTIR), UV-Vis diffuse reflectance spectroscopy (UVDRS), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and Mott-Schottky analyses. The photoelectrochemical sensing performance of SnO2/CuMnO2 microrods was 2.7 times higher than that of as-synthesized pure SnO2 microrods is due to the more visible light absorption ability and p-n heterojunction (synergy). The designed SnO2/CuMnO2/ITO sensor gives photocurrent signals for the detection of TC in the range of 0.01-1000 μM with the detection limit (LOD) of 5.6 nM. The practical applicability of the sensor was monitored in cow milk and the Taipei River water sample.
This study investigated on the co-pyrolysis of microalgae Chlorella vulgaris and high-density polyethylene (HDPE) waste mixtures which was performed with three types of catalysts, namely limestone (LS), HZSM-5 zeolite, and novel bi-functional LS/HZSM-5/LS. Kissinger-Kai (K-K) model-free method was coupled with Particle Swarm Optimization (PSO) model-fitting method using the thermogravimetric experimental data. A global sensitivity analysis was carried out using Latin Hypercube Sampling and rank transformation to assess the extent of impact of the input kinetic parameters on the output results. Furthermore, a thermodynamic analysis was performed to obtain parameters such as enthalpy change (ΔH), Gibb's free energy (ΔG), and entropy change (ΔS). The activation energy (EA) of the microalgae Chlorella vulgaris and HDPE binary mixture were found to be lower upon the addition of catalysts. Among the catalyst used, bi-functional LS/HZSM-5 catalyst exhibited the lowest EA (83.59 kJ/mol) and ΔH (78 kJ/mol) as compared to LS and HZSM-5 catalysts.
Solid acid catalyzed cracking of waste oil-derived fatty acids is an attractive route to hydrocarbon fuels. HZSM-5 is an effective acid catalyst for fatty acid cracking; however, its microporous nature is susceptible to rapid deactivation by coking. We report the synthesis and application of hierarchical HZSM-5 (h-HZSM-5) in which silanization of pre-crystallized zeolite seeds is employed to introduce mesoporosity during the aggregation of growing crystallites. The resulting h-HZSM-5 comprises a disordered array of fused 10-20 nm crystallites and mesopores with a mean diameter of 13 nm, which maintain the high surface area and acidity of a conventional HZSM-5. Mesopores increase the yield of diesel range hydrocarbons obtained from oleic acid deoxygenation from ~20% to 65%, attributed to improved acid site accessibility within the hierarchical network.
This study focused on producing high quality and yield of biodiesel from novel non-edible seed oil of abundantly available wild Raphnus raphanistrum L. using an efficient, recyclable and eco-friendly copper modified montmorillonite (MMT) clay catalyst. The maximum biodiesel yield of 83% was obtained by base catalyzed transesterification process under optimum operating conditions of methanol to oil ratio of 15:1, reaction temperature of 150 °C, reaction time of 5 h and catalyst loading of 3.5%. The synthesized catalyst and biodiesel were characterized for their structural features and chemical compositions using various state-of-the-art techniques, including x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H, 13C) and gas chromatography-mass spectroscopy. The fuel properties of the biodiesel were estimated including kinematic viscosity (4.36 cSt), density (0.8312 kg/L), flash point (72 °C), acid value (0.172 mgKOH/g) and sulphur content (0.0002 wt.%). These properties were compared and found in good agreement with the International Biodiesel Standards of American (ASTM-951, 6751), European Committee (EN-14214) and China GB/T 20828 (2007). The catalyst was re-used in five consecutive transesterification reactions without losing much catalytic efficiency. Overall, non-edible Raphnus raphanistrum L.. seed oil and Cu doped MMT clay catalyst appeared to be highly active, stable, and cheap contenders for future biofuel industry. However, detailed life cycle assessment (LCA) studies of Raphnus raphanistrum L. seed oil biodiesel are highly recommended to assess the technical, ecological, social and economic challenges.
In this study, the role of manganese precursors in mesoporous (meso) MnOx/γ-Al2O3 catalysts was examined systematically for toluene oxidation under ozone at ambient temperature (20 °C). The meso MnOx/γ-Al2O3 catalysts developed with Mn(CH3COO)2, MnCl2, Mn(NO3)2.4H2O and MnSO4 were prepared by an innovative single step solvent-deficient method (SDM); the catalysts were labeled as MnOx/Al2O3(A), MnOx/Al2O3(C), MnOx/Al2O3(N), and MnOx/Al2O3(S), respectively. Among all, MnOx/Al2O3(C) showed superior performance both in toluene removal (95%) as well as ozone decomposition (88%) followed by acetate, nitrate and sulphated precursor MnOx/Al2O3. The superior performance of MnOx/Al2O3(C) in the oxidation of toluene to COx is associated with the ozone decomposition over highly dispersed MnOx in which extremely active oxygen radicals (O2-, O22- and O-) are generated to enhance the oxidation ability of the catalysts greatly. In addition, toluene adsorption over acid support played a vital role in this reaction. Hence, the properties such as optimum Mn3+/Mn4+ ratio, acidic sites, and smaller particle size (≤2 nm) examined by XPS, TPD of NH3, and TEM results are playing vital role in the present study. In summary, the MnOx/Al2O3 (C) catalyst has great potential in environmental applications particularly for the elimination of volatile organic compounds with low loading of manganese developed by SDM.
Surface functionalization and shape modifications are the key strategies being utilized to overcome the limitations of semiconductors in advanced oxidation processes (AOP). Herein, the uniform α-Fe2O3 nanocrystals (α-Fe2O3-NCs) were effectively synthesized via a simple solvothermal route. Meanwhile, the sulfonic acid functionalization (SAF) and the impregnation of α-Fe2O3-NCs on g-C3N4 (α-Fe2O3-NCs@CN-SAF) were achieved through complete solvent evaporation technique. The surface functionalization of the sulfonic acid group on g-C3N4 accelerates the faster migration of electrons to the surface owing to robust electronegativity. The incorporation of α-Fe2O3-NCs with CN-SAF significantly enhances the optoelectronic properties, ultrafast spatial charge separation, and rapid charge transportation. The α-Fe2O3-HPs@CN-SAF and α-Fe2O3-NPs@CN-SAF nanocomposites attained 97.41% and 93.64% of Cr (VI) photoreduction in 10 min, respectively. The photocatalytic efficiency of α-Fe2O3-NCs@CN-SAF nanocomposite is 2.4 and 2.1 times higher than that of pure g-C3N4 and α-Fe2O3, respectively. Besides, the XPS, PEC and recycling experiments confirm the excellent photo-induced charge separation via Z-scheme heterostructure and cyclic stability of α-Fe2O3-NCs@CN-SAF nanocomposites.
Many attempts have been made to improve the photocatalytic performance of immobilized photocatalysts for large-scale applications by modification of the photocatalyst properties. In this work, immobilized bilayer photocatalyst composed of titanium dioxide (TiO2) and chitosan-montmorillonite (CS-MT) were prepared in a layer-by-layer arrangement supported on glass substrate. This arrangement allows a simultaneous occurrence of adsorption and photocatalysis processes of pollutants, whereby each layer could be independently modified and controlled to acquire the desired degree of occurring processes. It was found that the addition of MT clay within the CS composite sub-layer improved the mechanical strength of CS, reduced its swelling and shifted its absorption threshold to higher wavelengths. In addition, the band gap energy of the photocatalyst was also reduced to 2.93 eV. The immobilized TiO2/CS-MT exhibited methyl orange (MO) decolourization rate of 0.071 min-1 under light irradiation, which is better than the single TiO2 due to the synergistic processes of adsorption by CS-MT and photocatalysis by TiO2 layer. The MO dye took 6 h to achieve complete mineralization and produced sulfate and nitrate ions as the by-products. Furthermore, the immobilized TiO2/CS-MT could be reused for at least ten cycles of application without significant loss of its activity.
A unidirectional flow solar photocatalytic fuel cell (PFC) was successfully developed for the first time to offer alternative for electricity generation and simultaneous wastewater treatment. This study was focused on the synthesis of α-, δ- and β-MnO2 by wet chemical hydrothermal method for application as the cathodic catalyst in PFC. The crystallographic evolution was performed by varying the ratios of KMnO4 to MnSO4. The mechanism of the PFC with the MnO2/C as cathode was also discussed. Results showed that the catalytic activity of MnO2/C cathode was mainly predominated by their crystallographic structures which included Mn-O bond strength and tunnel size, following order of α- > δ- > β-MnO2/C. Interestingly, it was discovered that the specific surface areas (SBET) of different crystal phases did not give an impact on the PFC performance. However, the Pmax could be significantly influenced by the micropore surface area (Smicro) in the comparison among α-MnO2. Furthermore, the morphological transformation carried out by altering the hydrothermal duration demonstrated that the nanowire α-M3(24 h)/C with 1:1 ratio of KMnO4 and MnSO4 yielded excellent PFC performance with a Pmax of 2.8680 μW cm-2 and the lowest Rint of 700 Ω.
A continuous increase in the amount of greenhouse gases (GHGs) is causing serious threats to the environment and life on the earth, and CO2 is one of the major candidates. Reducing the excess CO2 by converting into industrial products could be beneficial for the environment and also boost up industrial growth. In particular, the conversion of CO2 into methanol is very beneficial as it is cheaper to produce from biomass, less inflammable, and advantageous to many industries. Application of various plants, algae, and microbial enzymes to recycle the CO2 and using these enzymes separately along with CO2-phillic materials and chemicals can be a sustainable solution to reduce the global carbon footprint. Materials such as MOFs, porphyrins, and nanomaterials are also used widely for CO2 absorption and conversion into methanol. Thus, a combination of enzymes and materials which convert the CO2 into methanol could energize the CO2 utilization. The CO2 to methanol conversion utilizes carbon better than the conventional syngas and the reaction yields fewer by-products. The methanol produced can further be utilized as a clean-burning fuel, in pharmaceuticals, automobiles and as a general solvent in various industries etc. This makes methanol an ideal fuel in comparison to the conventional petroleum-based ones and it is advantageous for a safer and cleaner environment. In this review article, various aspects of the circular economy with the present scenario of environmental crisis will also be considered for large-scale sustainable biorefinery of methanol production from atmospheric CO2.
To maximize the employment of sustainable solar energy in treating the recalcitrant pollutant and hydrogen energy production, the development of a highly efficient photocatalyst is desirable. Herein, a Z-scheme Ag/AgVO3/g-C3N4 photocatalyst was synthesized via a wet-impregnation method. The amount of Ag/AgVO3 deposited onto g-C3N4 has a significant effect on the photocharge carrier separation and migration of the as-developed Z-scheme photocatalyst. It was found that 0.5 wt % Ag/AgVO3/g-C3N4 photocatalyst exhibited a profound photocatalytic degradation performance with 82.6% ciprofloxacin removal and 3.57 mmol/h of hydrogen produced from natural rainwater under visible-light irradiation. Additionally, the apparent quantum efficiency (AQE) of this sample was 9.95% at 420 nm which is four times higher than the pure sample. The remarkable photocatalytic performance was attributed to the enhanced crystallographic structure, evidently from the XRD and XPS analysis. Moreover, the intimate contact between Ag/AgVO3 and g-C3N4 nanoparticles allows the smooth photocharge carrier separation and migrations, resulting in superior photocatalytic performance in comparison to the pure samples. Interestingly, the profound photocatalytic activity demonstrated here was achieved without the addition of any sacrificial reagents. This work demonstrates the feasibility of utilizing visible-light-driven photocatalysts in treating the recalcitrant antibiotic pollutants and producing hydrogen from natural rainwater.
Methylene blue is a refractory pollutant commonly present in textile wastewater. This study tests the feasibility of TiO2/graphene oxide (GO) composite in enhancing photocatalytic degradation of MB in synthetic wastewater with respect to scientific and engineering aspects. To enhance its removal, we vary the composition of the composite based on the TiO2 weight. Under UV-vis irradiation, the effects of photocatalyst's dose, pH, and reaction time on MB removal by the composites are evaluated under optimum conditions, while any changes in their physico-chemical properties before and after treatment are analyzed by using TEM, SEM, XRD, FTIR and BET. The photodegradation pathways of the target pollutant by the composite and its removal mechanisms are also elaborated. It is found that the same composite with a 1:2 wt ratio of GO/TiO2 has the largest surface area of 104.51 m2/g. Under optimum reactions (0.2 g/L of dose, pH 10, and 5 mg/L of pollutant's concentration), an almost complete MB removal could be attained within 4 h. This result is higher than that of the TiO2 alone (30%) under the same conditions. Since the treated effluents could meet the strict discharge standard limit of ≤0.2 μg/L set by China's regulation, subsequent biological treatments are unnecessary for completing biodegradation of remaining oxidation by-products in the wastewater effluents.
In this work, the photocatalytic property of p-type CuO was tailored by creating a heterojunction with n-type CdS. The CuO/CdS nanocomposite photocatalyst was synthesized by the ultrasound-assisted-wet-impregnation method and the physicochemical and optical properties of the catalysts were evaluated by using N2 physisorption, X-Ray Diffraction (XRD),X-Ray Photoelectron Spectroscopy (XPS), Raman spectroscopy, Transmission electron microscopy (TEM), Energy dispersive X-Ray (EDX) mapping, Field Emission Scanning Electron Microscope (FE-SEM), UV-Vis and photoluminescence spectroscopy experiments. Detailed characterization revealed the formation of a nanocomposite with a remarkable improvement in the charge carrier (electron/hole) separation. The photocatalytic degradation efficiencies of CuO and CuO/CdS were investigated for different dyes, for instance, rhodamine B (RhB), methylene blue (MLB), methyl blue (MB) and methyl orange (MO) under visible light irradiation. The obtained dye degradation efficiencies were ~93%, ~75%, ~83% and ~80%, respectively. The quantum yield for RhB degradation under visible light was 6.5 × 10-5. Reusability tests revealed that the CuO/CdS photocatalyst was recyclable up to four times. The possible mechanisms for the photocatalytic dye degradation over CuO/CdS nanocomposite were elucidated by utilizing various scavengers. Through these studies, it can be confirmed that the conduction band edges of CuO and CdS play a significant role in producing O2-. The produced O2- degraded the dye molecules in the bulk solution whereas the valence band position of CuO acted as the water oxidation site. In conclusion, the incorporation of CuO with CdS was demonstrated to be a viable strategy for the efficient photocatalytic degradation of dyes in aqueous solutions.
Catalytic cracking of vegetable oil mainly processed over zeolites, and among all the zeolites particularly HZMS-5 has been investigated on wide range for renewable and clean gasoline production from various plant oils. Despite the fact that HZSM-5 offers a higher conversion degree and boost aromatics yield, the isomerate yield reduces due to high cracking activity and shape selectivity of HZSM-5. Hence, to overcome these problems, in this study the transition metals, such as nickel and copper doped over HZSM-5 were tested for its efficiencies to improve the isoparaffin compounds. The catalysts were screened with linoleic acid in a catalytic cracking reaction conducted at 450 ᵒC for 90 min in an atmospheric condition in batch reactor. Then, the gasoline composition of the organic liquid product (OLP) was analysed in terms of paraffin, isoparaffin, olefin, naphthenes and aromatics (PIONA). The results showed that Cu/ZSM-5 produced the highest liquid yield of 79.1%, at the same time reduced the production of gas and coke to 18.8% and 0.7%. Furthermore, the desired isoparaffin composition in biogasoline increased from 1.6% to 6.8% and at the same time reduced the oxygenated and aromatic compounds to 15.4% and 59.7%, respectively. The linoleic acid as model compound of rubber seed oil, in the catalytic cracking reaction provides a clearer understanding of the process. Besides, the water gas shift (WGS) reaction in catalytic cracking reaction provides insitu hydrogen production to saturate the branched olefin into the desired isoparaffin and the aromatics into naphthenes.
Mesoporous carbon is a promising material having multiple applications. It can act as a catalytic support and can be used in energy storage devices. Moreover, mesoporous carbon controls body's oral drug delivery system and adsorb poisonous metal from water and various other molecules from an aqueous solution. The accuracy and improved activity of the carbon materials depend on some parameters. The recent breakthrough in the synthesis of mesoporous carbon, with high surface area, large pore-volume, and good thermostability, improves its activity manifold in performing functions. Considering the promising application of mesoporous carbon, it should be broadly illustrated in the literature. This review summarizes the potential application of mesoporous carbon in many scientific disciplines. Moreover, the outlook for further improvement of mesoporous carbon has been demonstrated in detail. Hopefully, it would act as a reference guidebook for researchers about the putative application of mesoporous carbon in multidimensional fields.
Cu doped InVO4 (xCu-InVO4 (x = 0.06-0.15 wt %) was synthesized by a facile one-pot hydrothermal method for the removal of methylene blue (MB) under LED light irradiation. The X-ray photoelectron spectroscopy (XPS) analysis indicated the coexistence of V5+ and V4+ species due to the O-deficient nature of the xCu-InVO4. The synthesized photocatalysts displayed a morphology of spherical and square shaped particles (20-40 nm) and micro-sized rectangle rods with a length range of 100-200 μm. The xCu-InVO4 exhibited superior adsorption and photodegradation efficiency compared to pristine InVO4 and TiO2 due to the presence of O2 vacancies, V4+/V5+ species, and Cu dopant. The optimum reaction conditions were found to be 5 mg L-1 (MB concentration), pH 6, and 100 mg of photocatalyst mass with a removal efficiency and mineralization degree of 100% and 96.67%, respectively. The main active species responsible for the degradation of MB were •OH radicals and h+. Reusability studies indicated that the 0.13Cu-InVO4 was deactivated after a single cycle of photocatalytic reaction due to significant leaching of V4+ and Cu2+ species.