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Thermally treated zeolitic imidazolate framework-8 (ZIF-8) for visible light photocatalytic degradation of gaseous formaldehyde.

ABSTRACT: The development of wide-spectrum responsive photocatalysts for efficient formaldehyde (HCHO) removal is highly desired yet remains a great challenge. Here we successfully converted zeolitic imidazolate framework-8 (ZIF-8), one of the most well-studied metal-organic frameworks (MOFs), from routine ultraviolet-driven to novel broad-spectrum-driven photocatalyst via a facile thermal treatment. The isocyanate groups (-N[double bond, length as m-dash]C[double bond, length as m-dash]O) formed in the thermally treated ZIF-8 (ZIF-8-T) is crucial in enabling the superior photocatalytic performance in formaldehyde degradation. Specifically, the best-performing ZIF-8-T sample showed around 2.1 and 9.4 times the HCHO adsorption amount and the solar photocatalytic degradation rate, respectively, of pristine ZIF-8. In addition, ZIF-8-T exhibited visible light (λ ≥ 400 nm) photocatalytic HCHO degradation performance, photo-converting 72% and nearly 100% of 20 ppm and 10 ppm HCHO within 1 hour, respectively. This work affords new insights and knowledge that inspire and inform the design and development of MOF-based photocatalysts with broad-spectrum responses for efficient air purification operations.

SUBMITTER: Wang T

PROVIDER: S-EPMC8159372 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Rhodamine B degradation by nanosized zeolitic imidazolate framework-8 (ZIF-8).

Project description:Adsorption and photodegradation of rhodamine B by ZIF-8 nanocrystals were studied using spectroscopic techniques coupled with density functional theory (DFT) cluster calculations. A fast adsorption rate was observed in the dark, but upon exposure to visible light or UV irradiation the adsorption rate noticeably increased. Although several studies previously reported this phenomenon involving bulk ZIF-8 powder, this is the first mechanistic study to our knowledge that demonstrates adsorption and degradation of rhodamine B by nanosized ZIF-8 under various light conditions. The combined study of N2 sorption pore analysis and surface-sensitive X-ray photoelectron spectroscopy (XPS) confirmed the surface adsorption was mainly due to the open metal sites and surface groups of nanoporous ZIF-8. The fluorescence studies suggested ZIF-8 nanocrystals were able to generate hydroxyl radicals in water but only under UV illumination. The work presented here provides an insight into understanding nanoscale metal-organic frameworks (MOFs) in the removal of organic molecules from wastewater.

| S-EPMC6088371 | biostudies-literature

Reversed Crystal Growth of RHO Zeolitic Imidazolate Framework (ZIF).

Project description:RHO zeolitic imidazolate framework (ZIF), Zn1.33 (O.OH)0.33 (nim)1.167 (pur), crystals with a rhombic dodecahedral morphology were synthesized by a solvothermal process. The growth of the crystals was studied over time using scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD) and Brunauer-Emmett-Teller (BET) analyses, and a reversed crystal growth mechanism was revealed. Initially, precursor materials joined together to form disordered aggregates, which then underwent surface recrystallization forming a core-shell structure, in which a disordered core is encased in a layer of denser, less porous crystal. When the growth continued, the shell became less and less porous, until it was a layer of true single crystal. The crystallization then extended from the surface to the core over a six-week period until, eventually, true single crystals were formed.

| S-EPMC4736437 | biostudies-literature

Visualization of gaseous iodine adsorption on single zeolitic imidazolate framework-90 particles.

Project description:Zeolitic imidazolate frameworks (ZIFs) are very useful as high-capacity iodine (I2) adsorbents. The adsorption performance is usually probed by measuring a statistical average property over an entire sample consisting of a large number of ZIF particles, leaving the interparticle heterogeneity information among individuals. Here we report a dark-field microscopy (DFM) method to visualize gaseous I2 adsorption on single ZIF-90 particles in situ and in real time. The adsorption of I2 is found to alter the scattering spectrum of ZIF-90 particles, inducing a distinct color change from bluewhite to yellow. According to correlating the adsorption amount of gaseous I2 with the change of B value from DFM images, we quantitatively image the adsorption process and estimate the related kinetic parameters at the single particle level. Single particle measurements clarify the large particle-to-particle heterogeneity in adsorption reactivity and significant adsorption activity improvement of ZIF-90 after introduction of linker defects, which provides a microscopic understanding of the structure-activity relationship. We further demonstrate the capacity of this strategy for studying gaseous I2 adsorption on single ZIF-91 particle as a derivative of ZIF-90 to illustrate the generality.

| S-EPMC8302588 | biostudies-literature

High-aspect ratio zeolitic imidazolate framework (ZIF) nanoplates for hydrocarbon separation membranes.

Project description:Metal-organic frameworks with high aspect ratios have the potential to yield high-performance gas separation membranes. We demonstrate the scalable synthesis of high–aspect ratio zeolitic imidazolate framework (ZIF)–8 nanoplates via a direct template conversion method in which high aspect ratio–layered Zn hydroxide sheets [Zn5(NO3)2(OH)8] were used as the sacrificial precursor. Successful phase conversion occurs as a result of the collaboration of low template stability and delayed delivery of 2-methylimidazole in weakly interacting solvents, particularly using acetone. When the ZIF-8 nanoplates with an average aspect ratio of 20 were shear aligned in the 6FDA-DAM polymer matrix by bar coating, the separation performance for propylene/propane far surpassed that of the previously reported mixed matrix and polymeric membranes, showing a propylene permeability of 164 Barrer and selectivity of 33.4 at 40 weight % loadings.

| S-EPMC8730619 | biostudies-literature

Thiosemicarbazone modified zeolitic imidazolate framework (TSC-ZIF) for mercury(ii) removal from water.

Project description:Zeolitic imidazolate frameworks (ZIF-8), and their derivatives, have been drawing increasing attention due to their thermal and chemical stability. The remarkable stability of ZIF-8 in aqueous and high pH environments renders it an ideal candidate for the removal of heavy metals from wastewater. In this study, we present the preparation of novel aldehyde-based zeolitic imidazolate frameworks (Ald-ZIF) through the integration of mixed-linkers: 2-methylimidazole (MIM) and imidazole-4-carbaldehyde (AldIM). The prepared Ald-ZIFs were post-synthetically modified with bisthiosemicarbazide (Bisthio) and thiosemicarbazide (Thio) groups, incorporating thiosemicarbazone (TSC) functionalities to the core of the framework. This modification results in the formation of TSC-functionalized ZIF derivatives (TSC-ZIFs). Thiosemicarbazones are versatile metal chelators, hence, adsorption properties of TSC-ZIFs for the removal of mercury(ii) from water were explored. Removal of mercury(ii) from homoionic aqueous solutions, binary and tertiary systems in competition with lead(ii) and cadmium(ii) under ambient conditions and neutral pH are reported in this study. MIM3.5:Thio1:Zn improved the removal efficiency of mercury(ii) from water, up to 97% in two hours, with an adsorption capacity of 1667 mg g-1. Desorption of mercury(ii) from MIM3.5:Thio1:Zn was achieved under acidic conditions, regenerating MIM3.5:Thio1:Zn for five cycles of mercury(ii) removal. TSC-ZIF derivatives, designed and developed here, represent a new class of dynamically functionalized adsorption material displaying the advantages of simplicity, efficiency, and reusability.

| S-EPMC9030954 | biostudies-literature

Hierarchical porous zeolitic imidazolate frameworks (ZIF-8) and ZnO@N-doped carbon for selective adsorption and photocatalytic degradation of organic pollutants.

Project description:Removing organic contaminants such as dyes from water is essential to purify wastewater. Herein, zeolitic imidazolate framework-8 (ZIF-8) and ZnO@N-doped C are reported as effective adsorbents and photocatalysts for the adsorption and degradation of organic dyes. The materials showed effective and selective adsorption toward anionic dyes such as methyl blue (MeB) dye in the presence of fluorescein (FLU) dye. The adsorption capacities of ZnO@N-doped C for MeB and FLU dyes are 900 mg g-1 and 100 mg g-1, respectively. According to UV-Vis diffuse reflectance spectroscopy (DRS) data, ZnO@N-doped C has a lower bandgap (2.07 eV) than ZIF-8 (4.34 eV) and ZnO (3.12 eV). Thus, ZnO@N-doped C serves as an effective photocatalyst for the degradation of both dyes under UV exposure. The degradation efficiency capacity of the dye (50 mg L-1) is >90% using 200 mg L-1 of the photocatalyst. The mechanism of adsorption and photocatalysis is investigated. The photodegradation pathway of the dye involved the generation of oxidative hydroxy radicals (OH˙), which can degrade the dyes. The degradation products of FLU were recorded using mass spectrometry.

| S-EPMC8982255 | biostudies-literature

Gold Nanorods (AuNRs) and Zeolitic Imidazolate Framework-8 (ZIF-8) Core-Shell Nanostructure-Based Electrochemical Sensor for Detecting Neurotransmitters.

Project description:The development of novel electrode materials for rapid and sensitive detection of neurotransmitters in the human body is of great significance for early disease diagnosis and personalized therapy. Herein, gold nanorod@zeolitic imidazolate framework-8 (AuNR@ZIF-8) core-shell nanostructures were prepared by controlled encapsulation of gold nanorods within a ZIF-8 assembly. The designed AuNR@ZIF-8 nanostructures have uniform morphology, good dispersion, a large specific surface area, and an average size of roughly 175 nm. Compared with individual ZIF-8 and AuNR-modified electrodes, the obtained core-shell-structured AuNR@ZIF-8 nanocomposite structure-modified electrode shows excellent electrocatalytic performance in the determination of dopamine (DA) and serotonin (ST). The designed AuNR@ZIF-8 exhibited a wide linear range of 0.1-50 μM and low detection limit (LOD, 0.03 μM, S/N = 3) for the determination of DA, as well as a linear range of 0.1-25 μM and low LOD (0.007 μM, S/N = 3) for monitoring ST. The improved performance is attributed to the synergistic effect of the high conductivity of AuNRs and multiple catalytic sites of ZIF-8. The good electroanalytical ability of AuNR@ZIF-8 for detection of DA and ST can provide a guide to efficiently and rapidly monitor other neurotransmitters and construct novel electrochemical sensors.

| S-EPMC8655944 | biostudies-literature

Optimized CO<sub>2</sub> Capture of the Zeolitic Imidazolate Framework ZIF-8 Modified by Solvent-Assisted Ligand Exchange.

Project description:Zeolitic imidazolate frameworks, like ZIF-8 and related structures, have shown great potential for the capture of carbon dioxide. Modifying their structure by exchanging part of the constituent organic ligands is a proven method for enhancing the capacity to absorb CO2. In this work, we performed solvent-assisted ligand exchange (SALE) on nanosized ZIF-8 (nZIF-8) with a series of functionalized imidazole derivatives (exchange percentages, after 24 h): 2-bromoimidazole (19%), 2-chloroimidazole (29%), 2-trifluoromethylbenzimidazole (4%), 2-mercaptobenzimidazole (4%), and 2-nitroimidazole (54%). The sodalite topology and porosity of nZIF-8 were maintained with all SALE modifications. Low-pressure CO2 adsorption of nZIF-8 (38.5 cm3 g-1) at STP was appreciably enhanced with all mixed-linker SALE products. Using halogenated (-Cl, -Br, and -CF3) imidazole derivatives in a 24 h SALE treatment resulted in increases between 11 and 22% in CO2 adsorption, while the thiol (-SH)- and nitro (-NO2)-functionalized SALE products led to 32 and 100% increases in CO2 uptakes, respectively. These CO2 uptakes were further optimized by varying the SALE treatment time. The SHbIm- and NO2Im-exchanged SALE products of nZIF-8 show 87 and 98 cm3 g-1 of CO2 uptakes after 60 and 120 h of SALE, respectively. These are record high CO2 adsorptions for all reported ZIF derivatives at low-pressure conditions.

| S-EPMC8412924 | biostudies-literature

Zeolitic Imidazolate Framework-8 (ZIF-8) as a Drug Delivery Vehicle for the Transport and Release of Telomerase Inhibitor BIBR 1532.

Project description:Telomerase is constitutively overexpressed in the majority of human cancers and telomerase inhibition provides a promising broad-spectrum anticancer therapeutic strategy. BIBR 1532 is a well-known synthetic telomerase inhibitor that blocks the enzymatic activity of hTERT, the catalytic subunit of telomerase. However, water insolubility of BIBR 1532 leads to low cellular uptake and inadequate delivery and thus, limits its anti-tumor effects. Zeolitic imidazolate framework-8 (ZIF-8) is considered as an attractive drug delivery vehicle for improved transport, release and anti-tumor effects of BIBR 1532. Herein, ZIF-8 and BIBR 1532@ZIF-8 were synthesized, respectively, and the physicochemical characterizations confirmed the successful encapsulation of BIBR 1532 in ZIF-8 coupled with an improved stability of BIBR 1532. ZIF-8 could alter the permeability of lysosomal membrane probably by the imidazole ring-dependent protonation. Moreover, ZIF-8 encapsulation facilitated the cellular uptake and release of BIBR 1532 with more accumulation in the nucleus. BIBR 1532 encapsulation with ZIF-8 triggered a more obvious growth inhibition of cancer cells as compared with free BIBR 1532. A more potent inhibition on hTERT mRNA expression, aggravated G0/G1 arrest accompanied with an increased cellular senescence were detected in BIBR 1532@ZIF-8-treated cancer cells. Our work has provided preliminary information on improving the transport, release and efficacy of water-insoluble small molecule drugs by using ZIF-8 as a delivery vehicle.

| S-EPMC10254680 | biostudies-literature

pH-triggered degradation and release of doxorubicin from zeolitic imidazolate framework-8 (ZIF8) decorated with polyacrylic acid.

Project description:Zeolite imidazolate framework-8 (ZIF8) represents a class of highly porous materials with a very high surface area, large pore volume, thermal stability, and biocompatibility. In this study, ZIF8-based nanostructures demonstrated a high loading capacity for doxorubicin (62 mg Dox per g ZIF8) through the combination of π-π stacking, hydrogen bonding, and electrostatic interactions. Dox-loaded ZIF8 was subsequently decorated with polyacrylic acid (PAA) (ZIF8-Dox@PAA) that showed good dispersity, fluorescent imaging capability, and pH-responsive drug release. The stable localization and association of Dox in ZIF8@PAA were investigated by C13 nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy. The NMR chemical shifts suggest the formation of hydrogen bonding interactions and π-π stacking interactions between the imidazole ring of ZIF8 and the benzene ring of Dox that can significantly improve the storage of Dox in the ZIF8 nanostructure. Additionally, the release mechanism of ZIF8-Dox@PAA was discussed based on the detachment of the PAA layer, enhanced solubility of Dox, and destruction of ZIF8 at different pH conditions. In vitro release test of ZIF8-Dox@PAA at pH 7.4 showed the low release rate of 24.7% even after 100 h. However, ZIF8-Dox@PAA at pH 4.0 exhibited four stages of release profiles, significantly enhanced release rate of 84.7% at the final release stage after 30 h. The release kinetics of ZIF8-Dox@PAA was analyzed by the sigmoidal Hill, exponential Weibull, and two-stage BiDoseResp models. The ZIF8-Dox@PAA nanocarrier demonstrated a promising theranostic nanoplatform equipped with fluorescent bioimaging, pH-responsive controlled drug release, and high drug loading capacity.

| S-EPMC8695245 | biostudies-literature

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