ABSTRACT
This study explores the modification of pore structures in porous silica materials synthesized using sodium silicate and waste gelatin, under varying silica-to-gelatin ratios. At ratios of 1.0-1.5, bimodal porous silica with mesopores and macropores emerged due to spaces between silica nanoparticles and clusters, following gelatin elimination. The study further evaluated the obtained bimodal porous silica as polyethyleneimine (PEI) supports for CO2 capture, alongside PEI-loaded unimodal porous silica and hollow silica sphere for comparison. Notably, the PEI-loaded bimodal silica showcased superior CO2 uptake, achieving 145.6â mg g-1 at 90 °C. Transmission electron microscopy (TEM) revealed PEI's uniform distribution within the pores of bimodal silica, unlike the excessive surface layering seen in unimodal silica. Conversely, PEI completely filled the hollow porous silica's interior, extending gas molecule diffusion distance. All sorbents displayed nearly constant CO2 adsorption across 20 cycles, demonstrating outstanding stability. Notably, the bimodal porous silica displayed a negligible capacity loss, underscoring its robust performance.
ABSTRACT
This study investigates the impact of microporous (SP-C) and micro-mesoporous carbon (DP-C) supports on the dispersion and phase transformation of iron oxides and their arsenic (V) removal efficiency. The research demonstrates that carbon-supported iron oxide sorbents exhibit superior As(V) uptake capacity compared to unsupported Fe2O3, attributed to reduced iron oxide crystallite sizes and As(V) adsorption on carbon supports. Maximum As(V) uptake capacities of 23.8 mg/g and 18.9 mg/g were achieved for Fe/SP-C and Fe/DP-C at 30 wt% and 50 wt% iron loading, respectively. The study reveals a nonlinear relationship between As(V) sorption capacity and iron oxide crystallite size after excluding As(V) adsorption capacity on carbon supports, suggesting the iron oxide phase (Fe3O4) plays a role in determining adsorption capacity. Iron oxide-loaded DP-C sorbents exhibit faster adsorption rates at low As(V) concentrations (5 mg/L) than SP-C sorbents due to their bimodal pore structure. Adsorption behavior varies at higher As(V) concentrations (45 mg/L), with Fe/DP-C reaching maximum capacity more slowly due to limited available adsorptive sites. All adsorbents maintained near-complete As(V) removal efficiency over five cycles. The findings provide insights for designing more efficient adsorbents for As(V) removal from contaminated water sources.
Subject(s)
Arsenic , Water Pollutants, Chemical , Water Purification , Carbon , Water Pollutants, Chemical/analysis , Kinetics , Arsenic/analysis , Iron/chemistry , Adsorption , WaterABSTRACT
Purification of As(V)-contaminated water through adsorption by Fe2O3-based materials is a promising technology due to its low-cost and high efficiency. Dispersing the Fe2O3 phase on silica supports can improve both the adsorption rate and capacity due to the reduction in Fe2O3 particle sizes and the prevention of clumping of the Fe2O3 particles. However, the clusters in conventional silica materials largely impede the diffusion of As(V) to reach the Fe2O3 sites dispersed inside the clusters. Here, by applying a gelatin template strategy, the structure of silica materials was tailored by changing the gelatin-to-silica ratio (0, 0.6, 1.2 and 1.8) and hydrothermal temperature (60 °C, 100 °C and 140 °C). The silica cluster size could be reduced using either a low gelatin-to-silica ratio (0.6) or a low hydrothermal temperature (60 °C). Increasing the gelatin-to-silica ratio to 1.2 created porous silica spheres with a hollow structure. The Fe2O3-loaded hollow porous silica spheres with a shell thickness of 280 nm had twice the maximum As(V) adsorption capacity (7.66 mg g-1) compared to the Fe2O3-loaded silica product prepared in the absence of gelatin (3.82 mg g-1). The maximum As(V) adsorption capacity could be further enhanced to 9.94 mg g-1 by reducing the shell thickness to 80 nm through increasing the gelatin-to-silica ratio to 1.8 and the hydrothermal temperature to 140 °C. In addition, the best Fe2O3-loaded hollow porous silica spheres had rapid As(V) adsorption and showed excellent durability as the As(V) removal efficiency slightly decreased to 98.9% subsequent to five adsorption-regeneration cycles.
Subject(s)
Silicon Dioxide , Wastewater , Ferric Compounds/chemistry , Gelatin , Porosity , Silicon Dioxide/chemistry , Wastewater/chemistry , WaterABSTRACT
Low cost Fe2O3-based sorbents with an exceptional selectivity toward the targeted As(V) pollutant have gained extensive attention in water treatment. However, their structural features often influence removal performance. In this respect, we present herein a rational design of silica-supported Fe2O3 sorbents with an enhanced morphological structure based on a simple temperature-induced process. Low-hydrothermal temperature synthesis (60 and 100 °C) provided a large silica-cluster size with a close packed structure (S-60 and S-100), contributing to an increase in mass transport resistance. Fe2O3/S-60 with 6.2-nm pore width silica achieved a maximum As(V) uptake capacity (qm) of only 3.5 mg g-1. Supporting Fe2O3 on S-100 with an approximately two-fold increase in the pore size (13 nm) did not lead to any evident enhancement in qe (3.7 mg g-1). However, expanding the pore window up to 22.6 nm (S-140) and 39.5 nm (S-180), along with changing from close-packed to sponge-like loose structures induced by high-temperature synthesis (140 °C and 180 °C), resulted in substantial increases in qm. Fe2O3/S-140 had 1.7 and 1.6 times higher qm (5.9 mg g-1) than Fe2O3/S-100 and Fe2O3/S-60, respectively. The highest qm (7.4 mg g-1) was achieved for Fe2O3/S-180, which was attributed to its relatively small-sized silica cluster and the largest cavities that facilitated easier access by As(V) to adsorbing sites.
Subject(s)
Water Pollutants, Chemical , Water Purification , Adsorption , Silicon Dioxide/chemistry , Temperature , Water Pollutants, Chemical/analysis , Water Purification/methodsABSTRACT
Arsenic (As) contamination in aqueous media is a major concern due to its adverse impacts on humans and the ecosystem more broadly because of its non-biodegradability. Consequently, an effective and selective sorbent is needed urgently to scavenge As pollutant. Herein, the adsorption behaviors of As(V) by Fe2O3 and Fe2O3 supported on different silica materials, consisting of unimodal mesoporous silica (Fe2O3/U-SiO2) and dual meso-macroporous silica (Fe2O3/B-SiO2), were compared to examine their structure-efficiency relationships in the elimination of As(V). Fe2O3/B-SiO2 was much faster at As(V) removal and had an impressively higher uptake capability, reaching nearly 50% and 2.5 mg g-1 within 5 min compared to bare Fe2O3 (6% and 0.3 mg g-1) and Fe2O3/U-SiO2 (11.9% and 0.59 mg g-1). These better results were because of the highly dispersed Fe2O3 nanoparticles on the B-SiO2 support that provided abundant reactive sites as well as a macropore structure facilitating As(V) diffusion into adsorptive sites. The maximum adsorptive capacity of Fe2O3/B-SiO2 (4.7 mg As per 1 g adsorbent) was 1.3- and 1.7-fold greater than for Fe2O3/U-SiO2 and Fe2O3, respectively. The outstanding performance and reusability of Fe2O3/B-SiO2 with its ease of production, economical and environmentally friendly features made it even more attractive for As(V) remediation. The explored relationship between the structure of SiO2-supported Fe2O3 sorbents and their performance in removing As(V) could be informative for the future design of highly efficient adsorbents for the decontamination of water.
Subject(s)
Arsenic , Environmental Pollutants , Water Pollutants, Chemical , Adsorption , Arsenic/chemistry , Ecosystem , Ferric Compounds/chemistry , Humans , Silicon Dioxide , Water/chemistry , Water Pollutants, Chemical/analysisABSTRACT
Recycling of waste glycerol derived from biodiesel production to high value-added chemicals is essential for sustainable development of Bio-Circular-Green Economy. This work studied the conversion of glycerol to 1,3-propanediol over Pt/WOx/Al2O3 catalysts, pointing out the impacts of catalyst pore sizes and operating conditions for maximizing the yield of 1,3-propanediol. The results suggested that both pore confinement effect and number of available reactive metals as well as operating conditions determined the glycerol conversion and 1,3-propanediol selectivity. The small-pore 5Pt/WOx/S-Al2O3 catalyst (6.1 nm) gave a higher Pt dispersion (32.0%), a smaller Pt crystallite size (3.5 nm) and a higher number of acidity (0.47 mmol NH3 g-1) compared to those of the large-pore 5Pt/WOx/L-Al2O3 catalyst (40.3 nm). However, glycerol conversion and 1,3-propanediol yield over the small-pore 5Pt/WOx/S-Al2O3 catalyst were significantly lower than those of the large-pore Pt/WOx/L-Al2O3 catalyst, suggesting that the diffusional restriction within the small-pore catalyst suppressed transportation of molecules to expose catalytic active sites, favoring the excessive hydrogenolysis of 1,3-propanediol, giving rise to undesirable products. The best 1,3-propanediol yield of 32.8% at 78% glycerol conversion were achieved over the 5Pt/WOx/L-Al2O3 under optimal reaction condition of 220 °C, 6 MPa, 5 h reaction time and amount of catalyst to glycerol ratio of 0.25 g mL-1. However, the 1,3-propanediol yield and glycerol conversion decreased to 19.6% and 51% after the 4th reaction-regeneration which were attributed to the carbonaceous deposition and the agglomeration of Pt particles.
Subject(s)
Glycerol , Propylene Glycol , Catalysis , Propylene GlycolsABSTRACT
Impact of pore characteristics of porous silica supports on loading capacity and release behavior of ibuprofen was investigated. The porous silica materials and ibuprofen-loaded porous silica materials were thoroughly characterized by N2-sorption, thermal gravimetric and derivative weight analyses (TG-DTW), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM) to determine the physical properties of materials, amount of ibuprofen adsorbed and position of ibuprofen. The detailed characterization reveals that the ibuprofen molecules adsorbed inside the mesopores. Increasing the mesopore size from 5nm to 10nm increased the ibuprofen loading from 0.74 to 0.85mmol/g, respectively. Incorporation of macropore into the structure of porous silica materials enhanced the ibuprofen loading capacity of 11.8-20.3%. The ibuprofen-loaded bimodal meso-macroporous silica materials exhibited the highest dissolution of 92wt.% within an hour. The ibuprofen particles deposited on the external surface of the porous silica materials showed a lower dissolution rate than the ibuprofen adsorbed inside the mesopores due to the formation of ibuprofen crystalline.