Browse
Submit Data
Databases
API
Help

Dataset Information

23 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-organic framework membranes with single-atomic centers for photocatalytic CO₂ and O₂ reduction.

ABSTRACT: The demand for sustainable energy has motivated the development of artificial photosynthesis. Yet the catalyst and reaction interface designs for directly fixing permanent gases (e.g. CO₂, O₂, N₂) into liquid fuels are still challenged by slow mass transfer and sluggish catalytic kinetics at the gas-liquid-solid boundary. Here, we report that gas-permeable metal-organic framework (MOF) membranes can modify the electronic structures and catalytic properties of metal single-atoms (SAs) to promote the diffusion, activation, and reduction of gas molecules (e.g. CO_2, O₂) and produce liquid fuels under visible light and mild conditions. With Ir SAs as active centers, the defect-engineered MOF (e.g. activated NH₂-UiO-66) particles can reduce CO₂ to HCOOH with an apparent quantum efficiency (AQE) of 2.51% at 420 nm on the gas-liquid-solid reaction interface. With promoted gas diffusion at the porous gas-solid interfaces, the gas-permeable SA/MOF membranes can directly convert humid CO₂ gas into HCOOH with a near-unity selectivity and a significantly increased AQE of 15.76% at 420 nm. A similar strategy can be applied to the photocatalytic O₂-to-H₂O₂ conversions, suggesting the wide applicability of our catalyst and reaction interface designs.

SUBMITTER: Hao YC

PROVIDER: S-EPMC8113524 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction.

Project description:A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3 (4,4'-dcbpy)] and a photosensitizer [Ru(bpy)2 (5,5'-dcbpy)]Cl2 using the isoreticular series of metal-organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location-either at the outer MOF particle surface or inside the MOF cavities-affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.

| S-EPMC8453824 | biostudies-literature

Application of a Mixed-Ligand Metal-Organic Framework in Photocatalytic CO2 Reduction, Antibacterial Activity and Dye Adsorption.

Project description:In this paper, a known mixed-ligand MOF {[Co2(TZMB)2(1,4-bib)0.5(H2O)2]·(H2O)2}n (compound 1) was reproduced, and its potential application potential was explored. It was found that compound 1 had high photocatalytic activity for CO2 reduction. After 12 h of illumination, the formation rate of CO, which is the product of CO2 reduction by compound 1, reached 3012.5 μmol/g/h. At the same time, compound 1 has a good antibacterial effect on Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Candida albicans (C. albicans), which has potential research value in the medical field. In addition, compound 1 can effectively remove Congo Red from aqueous solutions and achieve the separation of Congo red from mixed dye solutions.

| S-EPMC10343588 | biostudies-literature

High selectivity of photocatalytic reduction of CO2 to CO based on terpyridine ligand supported CuI metal organic framework.

Project description:In this work, a 4'-(4-cynaophenyl)-4,2':6',4-terpyridine supported CuI MOFs photocatalyst (Cu I MOF) was applied to the photocatalytic CO2 reduction for the first time. The micro-structural and physicochemical properties of the Cu I MOF were systematically studied by the powder X-ray diffraction (PXRD), Single crystal X-ray diffraction (SCXRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), UV-Vis diffuse spectroscopy (UV-vis DRS), ns-level photoluminescence spectra (ns-level PL), Ultraviolet photoelectron spectroscopy (UPS), and N2 adsorption-desorption test (BET-BJH). Moreover, the in situ diffuse reflectance infrared fourier transform spectroscopy (in situ DRIFTS) was applied to investigate the adsorption and reaction intermediates of photocatalytic CO2 reduction. As a result, Cu I MOF exhibited good performance and outstanding selectivity toward photocatalytic reduction of CO2 to CO under full-spectrum and visible light illumination. Notably, 100% selective photocatalytic conversion of CO2 to CO was achieved. Thus, the study presents the high selectivity and CO2 reduction efficiency of Cu I MOF as a potential family of photocatalysts.

| S-EPMC9388720 | biostudies-literature

Selective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation.

Project description:The efficient use of renewable X/γ-rays or accelerated electrons for chemical transformation of CO2 and water to fuels holds promise for a carbon-neutral economy; however, such processes are challenging to implement and require the assistance of catalysts capable of sensitizing secondary electron scattering and providing active metal sites to bind intermediates. Here we show atomic Cu-Ni dual-metal sites embedded in a metal-organic framework enable efficient and selective CH3OH production (~98%) over multiple irradiated cycles. The usage of practical electron-beam irradiation (200 keV; 40 kGy min-1) with a cost-effective hydroxyl radical scavenger promotes CH3OH production rate to 0.27 mmol g-1 min-1. Moreover, time-resolved experiments with calculations reveal the direct generation of CO2•‒ radical anions via aqueous electrons attachment occurred on nanosecond timescale, and cascade hydrogenation steps. Our study highlights a radiolytic route to produce CH3OH with CO2 feedstock and introduces a desirable atomic structure to improve performance.

| S-EPMC10409780 | biostudies-literature

Metal-organic framework derived single-atom catalysts for electrochemical CO2 reduction.

Project description:With maximum atomic utilization, transition metal single atom catalysts (SACs) show great potential in electrochemical reduction of CO2 to CO. Herein, by a facile pyrolysis of zeolitic imidazolate frameworks (ZIFs) assembled with tiny amounts of metal ions, a series of metal-nitrogen-carbon (M-N-C) based SACs (M = Fe, Ni, Mn, Co and Cu), with metal single atoms decorated on a nitrogen-doped carbon support, have been precisely constructed. X-ray photoelectron spectroscopy (XPS) for M-N-C showed that the N 1s spectrum was deconvoluted into five peaks for pyridinic (∼398.3 eV), M-N coordination (∼399.6 eV), pyrrolic (∼400.4 eV), quaternary (∼401.2 eV) and oxidized (∼402.9 eV) N species, demonstrating the existence of M-N bonding. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) indicates homogeneous distribution of metal species throughout the N-doped carbon matrix. Among the catalysts examined, the Fe-N-C catalyst exhibits the best catalytic performance in electrocatalytic CO2 reduction reaction (CO2RR) with nearly 100% faradaic efficiency for CO (FECO) at -0.9 V vs. the reversible hydrogen electrode (RHE). Ni-N-C is the second most active catalyst towards CO2RR performance, then followed by Mn-N-C, Co-N-C and Cu-N-C. Considering the optimum activity of Fe-N-C catalyst for the CO2RR, we then further investigate the effect of pyrolysis temperature on CO2RR of the Fe-N-C catalyst. We find the Fe-N-C catalyst pyrolyzed at 1000 °C exhibits the best catalytic activity in CO2RR with excellent CO selectivity.

| S-EPMC9661489 | biostudies-literature

Photocatalytic CO2 reduction using La-Ni bimetallic sites within a covalent organic framework.

Project description:The precise construction of photocatalysts with diatomic sites that simultaneously foster light absorption and catalytic activity is a formidable challenge, as both processes follow distinct pathways. Herein, an electrostatically driven self-assembly approach is used, where phenanthroline is used to synthesize bifunctional LaNi sites within covalent organic framework. The La and Ni site acts as optically and catalytically active center for photocarriers generation and highly selective CO2-to-CO reduction, respectively. Theory calculations and in-situ characterization reveal the directional charge transfer between La-Ni double-atomic sites, leading to decreased reaction energy barriers of *COOH intermediate and enhanced CO2-to-CO conversion. As a result, without any additional photosensitizers, a 15.2 times enhancement of the CO2 reduction rate (605.8 μmol·g-1·h-1) over that of a benchmark covalent organic framework colloid (39.9 μmol·g-1·h-1) and improved CO selectivity (98.2%) are achieved. This work presents a potential strategy for integrating optically and catalytically active centers to enhance photocatalytic CO2 reduction.

| S-EPMC10148855 | biostudies-literature

Photocatalytic CO2 reduction with aminoanthraquinone organic dyes.

Project description:The direct utilization of solar energy to convert CO2 into renewable chemicals remains a challenge. One essential difficulty is the development of efficient and inexpensive light-absorbers. Here we show a series of aminoanthraquinone organic dyes to promote the efficiency for visible light-driven CO2 reduction to CO when coupled with an Fe porphyrin catalyst. Importantly, high turnover numbers can be obtained for both the photosensitizer and the catalyst, which has not been achieved in current light-driven systems. Structure-function study performed with substituents having distinct electronic effects reveals that the built-in donor-acceptor property of the photosensitizer significantly promotes the photocatalytic activity. We anticipate this study gives insight into the continued development of advanced photocatalysts for solar energy conversion.

| S-EPMC9968311 | biostudies-literature

Application of a Metal Cobalt Based on 4,6-Bis(imidazol-1-yl)isophthalicacid Metal-Organic -Framework Materials in Photocatalytic CO2 Reduction, Antibacterial, and Dye Adsorption.

Project description:In this paper, the reported MOF ([Co(bimip)(H2O)0.5]·0.5H2O) was employed in photocatalytic CO2 reduction, antibacterial, and dye adsorption experiments. The photocatalytic activity of the MOF for CO2 reduction was systematically investigated. The high average CO generation rate of 3421.59 μmol·g-1·h-1 after 12 h confirms the efficient photocatalytic CO2 reduction ability of the MOF. At the same time, the MOF can completely inhibit the growth of S. aureus and C. albicans within 24 h when its concentration reaches 400 μg/mL and 500 μg/mL, respectively. The MOF has an adsorption capacity for CR. The adsorption rate was 83.42% at 60 min, and the adsorption capacity of the MOF for CR reached 500.00 mg·g-1.

| S-EPMC10537682 | biostudies-literature

GO-guided direct growth of highly oriented metal-organic framework nanosheet membranes for H2/CO2 separation.

Project description:Highly oriented, ultrathin metal-organic framework (MOF) membranes are attractive for practical separation applications, but the scalable preparation of such membranes especially on standard tubular supports remains a huge challenge. Here we report a novel bottom-up strategy for directly growing a highly oriented Zn2(bIm)4 (bIm = benzimidazole) ZIF nanosheet tubular membrane, based on graphene oxide (GO) guided self-conversion of ZnO nanoparticles (NPs). Through our approach, a thin layer of ZnO NPs confined between a substrate and a GO ultrathin layer self-converts into a highly oriented Zn2(bIm)4 nanosheet membrane. The resulting membrane with a thickness of around 200 nm demonstrates excellent H2/CO2 gas separation performance with a H2 performance of 1.4 × 10-7 mol m-2 s-1 Pa-1 and an ideal separation selectivity of about 106. The method can be easily scaled up and extended to the synthesis of other types of Zn-based MOF nanosheet membranes. Importantly, our strategy is particularly suitable for the large-scale fabrication of tubular MOF membranes that has not been possible through other methods.

| S-EPMC5941280 | biostudies-literature

Large-Scale Screening and Machine Learning for Metal-Organic Framework Membranes to Capture CO2 from Flue Gas.

Project description:To combat global warming, as an energy-saving technology, membrane separation can be applied to capture CO2 from flue gas. Metal-organic frameworks (MOFs) with characteristics like high porosity have great potential as membrane materials for gas mixture separation. In this work, through a combination of grand canonical Monte Carlo and molecular dynamics simulations, the permeability of three gases (CO2, N2, and O2) was calculated and estimated in 6013 computation-ready experimental MOF membranes (CoRE-MOFMs). Then, the relationship between structural descriptors and permeance performance, and the importance of available permeance area to permeance performance of gas molecules with smaller kinetic diameters were found by univariate analysis. Furthermore, comparing the prediction accuracy of seven classification machine learning algorithms, XGBoost was selected to analyze the order of importance of six structural descriptors to permeance performance, through which the conclusion of the univariate analysis was demonstrated one more time. Finally, seven promising CoRE-MOFMs were selected, and their structural characteristics were analyzed. This work provides explicit directions and powerful guidelines to experimenters to accelerate the research on membrane separation for the purification of flue gas.

| S-EPMC9321510 | biostudies-literature