Copper (Cu, 1-5 wt%) was loaded onto carbon nanotubes (CNTs) by a simple electrochemical method. The physicochemical properties of catalysts (Cu/CNTs) were characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen (N2) adsorption-desorption, Fourier transform infra-red spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electron spinning resonance (ESR). The results showed that the Cu was distributed well on the CNT surface by the interaction of Cu(2+) ions with -OH and -COOH groups on the CNT surface, which preferentially occurred at the defect sites along the CNT backbone. The Cu-O-C bonds formed were found to play an important role in enhancing the photoactivity of the catalysts. The highest number of Cu-O-C bonds possessed by 3 wt% Cu/CNTs demonstrated the best performance in the degradation of p-chloroaniline (96%) under UV light irradiation within 5 h of reaction at 27 °C and under neutral pH conditions. Kinetic studies showed that the degradation followed the pseudo-first order model and the surface reaction was the controlling step. It is believed that these results could contribute to the synthesis of various supported catalysts for various applications.
Photocatalytic degradation is a valuable direction for eliminating organic pollutants in the environment because of its exceptional catalytic activity and low energy requirements. As one of the prospective photocatalysts, zirconium dioxide (ZrO2) is a promising candidate for photoactivity due to its favorable redox potential and higher chemical stability. ZrO2 has a high rate of electron-hole recombination and poor light-harvesting capabilities. Still, modification has demonstrated enhancements, especially extra-modification, and is therefore worthy of investigation. This present review provides a comprehensive overview of the extra-modifications of ZrO2 for enhanced photocatalytic performance, including coupling with other semiconductors, doping with metal, non-metal, and co-doping with metal and non-metal. The extra-modified ZrO2 showed superior performance in degrading the organic pollutant, particularly dyes and phenolic compounds. Interestingly, this review also briefly highlighted the probable mechanisms of the extra-modification of ZrO2 such as p-n heterojunction, type II heterojunction, and Z-scheme heterojunction. The latter heterojunction with excellent electron-hole space separation improved the photoactivity. Extensive research on ZrO2's photocatalytic potential is presented, including the removal of heavy metals, the redox of heavy metals and organic pollutants, and the evolution of hydrogen. Modified ZrO2's photocatalytic effectiveness depends on its band position, oxygen vacancy concentration, and metal defect sites. The opportunities and future problems of the extra-modified ZrO2 photocatalyst are also discussed. This review aims to share knowledge regarding extra-modified ZrO2 photocatalysts and inspire new environmental remediation applications.
Electronic waste has become a global concern, as it has been steadily increasing over the years. The lack of regulation and appropriate processing facilities has rendered these wastes an environmental hazard. However, they represent excellent alternative sources of precious metals, which are highly in demand in various industries. Adsorption has been a popular method for metal removal/recovery because of several advantages, such as ease of use and low cost. In this regard, it is crucial to develop an inexpensive and functionalized adsorbent to selectively adsorb precious metals. Thus, silica, which is derived from rice husk and is abundantly present in Indonesia, was functionalized using an ionic liquid (SiRH_Im) and used for Au(III) adsorption from a simulated mobile phone leach liquor. SiRH_Im exhibited a high adsorption capacity (232.5 mg g-1). The Au(III) adsorption kinetic suitably fitted with the pseudo-second-order kinetic model. The Au(III) adsorption followed a chemisorption route that suited the monolayer model. Thomas' and Yoon-Nelson's models were well suited for the continuous Au(III) behavior. Selective recovery of Au(III) from SiRH_Im was achieved via sequential desorption. SiRH_Im also showed excellent reusability, as indicated by a negligible decrease in adsorptive performance over three cycles. The functionalization of silica derived from rice husk using an ionic liquid led to the successful creation of a solid adsorbent with a high adsorption capacity toward precious metals present in a simulated leach solution. Our results highlight the benefit of the functionalization of biomass through the immobilization of an ionic liquid toward the enhancement of its adsorption capability.
Fibrous silica-titania (FST) catalysts were synthesized by microemulsion followed by silica seed-crystal crystallization methods under various molar ratios of toluene to water (T/W). The catalysts were characterized by XRD, UV-DRS, FESEM, TEM, AFM, N2 adsorption-desorption, FTIR, and ESR. The results revealed that altering the T/W ratio affected the growth of the silica and titania and led to different size, fiber density, silica-titania structure, and number of hydroxyl groups, as well as oxygen vacancies in the FSTs, which altered their behavior toward subsequent application. Photodegradation of ibuprofen (IBP) are in the following order: FST(6:1) (90%) > FST(5:1) (84%) > FST(7:1) (79%) > commercial TiO2 (67%). A kinetics study using Langmuir-Hinshelwood model illustrated that the photodegradation followed the pseudo-first-order and adsorption was the rate-limiting step. Optimization by response surface methodology (RSM) showed that the pH, initial concentration, and catalyst dosage were the remarkable parameters in photodegradation of IBP. The FST (6:1) maintained its photocatalytic activities for up to five cycles reaction without serious catalyst deactivation, and was also able to degrade other endocrine-disrupting chemicals, indicating its potential use for the treatment of those chemicals in wastewater.
Ternary CuO/AgO/FSZr photocatalysts were fabricated via the hydrothermal and electrochemical methods with three different CuO loading (1, 3 and 5 wt%), indicated as 1CuO/AgO/FSZr, 3CuO/AgO/FSZr and 5CuO/AgO/FSZr. The photocatalytic reaction was tested towards simultaneous chromium (VI) photoreduction and p-cresol photooxidation and the performance in order as follow: 3CuO/AgO/FSZr > 5CuO/AgO/FSZr > 1CuO/AgO/FSZr > AgO/FSZr > FSZr. CuO/AgO/FSZr photocatalysts showed an improvement in photocatalytic activity compared to AgO/FSZr and FSZr due to the reduction potential of chromium (VI) aligned closer to the conduction band of CuO and provided abundant free active electrons (e-) and holes (h+) with efficient transportation and migration. Interestingly, the 3CuO/AgO/FSZr was established as the best photocatalyst with 98% reduction of chromium (VI) and 83% oxidation of p-cresol simultaneously, owing to its strong corporation between the metal oxides and support and higher total pore volume. The Langmuir-Hinshelwood model were employed for kinetics which followed the pseudo-first-order kinetics model well. Based on the simultaneous photocatalytic mechanism, chromium (VI) and p-cresol were directly reduced and oxidized by e- and h+, respectively. The response surface methodology (RSM) discovered that the quadratic term initial concentration of chromium (VI) is the main significant factor in photocatalytic performance. The optimum parameters for simultaneous photoredox of chromium (VI) and p-cresol predicted from RSM are 9.6 mg L-1 of chromium (VI) concentration, 9.8 mg L-1 of p-cresol concentration and 0.32 g L-1 of catalyst dosage. Under these conditions the error between the predicted and experimental values is only 3.7%. The 3CuO/AgO/FSZr sustained the photocatalytic performance after reused for five cycles and could oxidized various organic pollutants as well as reduced chromium (VI) simultaneously.
The fatty acid methyl ester (FAME) production from dairy effluent scum as a sustainable energy source using CaO obtained from organic ash over titanium dioxide nanoparticles (TNPs) as the transesterification nano-catalyst has been studied. The physical and chemical properties of the synthesized catalysts were characterized, and the effect of different experimental factors on the biodiesel yield was studied. It was revealed that the CaO-TiO2 nano-catalyst displayed bifunctional properties, has both basic and acid phases, and leads to various effects on the catalyst activity in the transesterification process. These bifunctional properties are critical for achieving simultaneous transesterification of dairy scum oil feedstock. According to the reaction results, the catalyst without and with a low ratio of TNPs showed a low catalytic activity. In contrast, the 3Ca-3Ti nano-catalyst had the highest catalytic activity and a strong potential for reusability, producing a maximum biodiesel yield of 97.2% for a 3 wt% catalyst, 1:20 oil to methanol molar ratio for the dairy scum, and a reaction temperature of 70 °C for a period of 120 min under a 300 kPa pressure. The physical properties of the produced biodiesel are within the EN14214 standards.
Biogas consisting of carbon dioxide/methane (CO2/CH4) gas mixtures has emerged as an alternative renewable fuel to natural gas. The presence of CO2 can decrease the calorific value and generate greenhouse gas. Hence, separating CO2 from CH4 is a vital step in enhancing the use of biogas. Zeolite and zeolite-based mixed matrix membrane (MMM) is considered an auspicious candidate for CO2/CH4 separation due to thermal and chemical stability. This review initially addresses the development of zeolite and zeolite-based MMM for the CO2/CH4 separation. The highest performance in terms of CO2 permeance and CO2/CH4 selectivity was achieved using zeolite and zeolite-based MMM, which exhibited CO2 permeance in the range of 2.0 × 10- 7-7.0 × 10- 6 mol m- 2 s- 1 Pa- 1 with CO2/CH4 selectivity ranging from 3 to 300. Current trends directed toward improving CO2/CH4 selectivity via modification methods including post-treatment, ion-exchanged, amino silane-grafted, and ionic liquid encapsulated of zeolite-based MMM. Those modification methods improved the defect-free and interfacial adhesions between zeolite particulates and polymer matrices and subsequently enhanced the CO2/CH4 selectivity. The modifications via ionic liquid and silane methods more influenced the CO2/CH4 selectivity with 90 and 660, respectively. This review also focuses on the possible applications of zeolite-based MMM, which include the purification and treatment of water as well as biomedical applications. Lastly, future advances and opportunities for gas separation applications are also briefly discussed. This review aims to share knowledge regarding zeolite-based MMM and inspire new industrial applications.
Vanadia (V2O5)-incorporated fibrous silica-titania (V/FST) catalysts, which were successfully synthesized using a hydrothermal method followed by the impregnation of V2O5. The catalysts were then characterized using numerous techniques, including X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption analyses, ultraviolet-visible diffuse reflectance spectroscopy, Fourier-transform infrared, X-ray photoelectron spectroscopy, and photoluminescence (PL) analyses. The study found that varying the amount of V2O5 (1-10 wt%) had a significant impact on the physicochemical properties of the FST, which in turn improved the photodegradation efficiency of two organic compounds, ciprofloxacin (CIP) and congo red (CR). 5V/FST demonstrated the best performance in degrading 10 mg L-1 of CIP (83%) and CR (100%) at pH 3 using 0.375 g L-1 catalyst under visible light irradiation within 180 min. The highest photoactivity of 5V/FST is mainly due to higher crystallinity and the highest number of V2O5-FST interactions. Furthermore, as demonstrated by PL analysis, the 5V/FST catalyst has the most significant impact on interfacial charge transfer and reduces electron-hole recombination. The photodegradation of both contaminants follows the Langmuir-Hinshelwood pseudo-first-order model, according to the kinetic study. The scavenger investigation demonstrated that hydroxyl radicals and holes dominated species in the system, indicating that the catalyst effectively generated reactive species for pollutant degradation. A possible mechanism was also identified for FST and 5V/FST. Interestingly, V2O5 acts as an electron-hole recombination inhibitor on FST for selective hole oxidation of ciprofloxacin and congo red photodegradation. Finally, the degradation efficiency of the catalyst remained relatively stable even after five cyclic experiments, indicating its potential for long-term use in environmental remediation.