MOF-derived Nanoporous Carbon Research Articles

In-situ synthesis of high-quality porous Co-NC@MoS2 composites

MOF-derived nanoporous carbon materials and TMDCs are promising candidates for catalytical applications in many fields, such as photovoltaic devices and lithium-sulfur batteries. Traditional TMDCs catalysts suffer from low conductivity and poor catalytic activity, making it difficult to meet industrial applications. Here, Co-NC@MoS2 composite materials were successfully prepared by chemical vapor deposition technology, which exhibit the high electrocatalytic activity, good charge transport ability, multiple internal channels and excellent electrical conductivity due to the dual advantages of two materials. The composite is expected to be applied in energy catalysis fields such as quantum dot sensitized solar cells.

Multiplex signal amplification for ultrasensitive CRP assay via integrated electrochemical biosensor array using MOF-derived carbon material and aptamers

Accurate and precise detection of disease-associated proteins, such as C-reactive protein (CRP), remains a challenge in biosensor development. Herein, we present a novel approach－an integrated disposable aptasensor array－designed for precise, ultra-sensitive, and parallel detection of CRP in plasma samples. This integrated biosensing array platform enables multiplex parallel testing, ensuring the accuracy and reliability in sample analysis. The ultra-sensitivity of this biosensor is achieved through multiplex signal amplification. Leveraging the superior conductivity and extensive surface area of MOF-derived nanoporous carbon material (CMOF), the biosensor enhances recognition elements (aptamers) by catalyzing the horseradish peroxidase (HRP) label enzyme reaction to multiply the number of probe molecules. Optimized conditions yielded exceptional performance, exhibiting high accuracy (relative standard deviation, RSD≤10.0 %), a low detection limit (0.3 pg/mL, S/N = 3), ultra-sensitivity (0.16 μA/ng mL−1 mm−2), and a rapid response (seven parallel tests within 60 min). Importantly, this multi-unit integrated disposable aptasensor array accurately quantified CRP in human serum, demonstrating comparable results to commercial enzyme–linked immunosorbent assay (ELISA). This technology showcases promise for detecting various biomarkers using a unified approach, presenting an appealing strategy for early disease diagnosis and biological analysis.

MOF-Derived Nanoporous Carbon As an Efficient Bifunctional Oxygen Electrocatalyst for Erzabs

Zinc-air batteries are cost-effective batteries that possess a high energy density (1086 Wh Kg-1), compared to other conventional battery systems. In order to improve the electrochemical performance of electrically rechargeable zinc-air batteries (ERZABs), an effective bifunctional oxygen electrocatalyst is required. Hence, the development of non-noble metal bifunctional catalysts for ORR and OER is of prime importance. The transition metal-based catalysts have increasing demand since they are promising alternatives, in terms of cost and durability, to noble metal catalysts. Metal-organic frameworks (MOF) based catalysts show high catalytic activity due to adjustable pore size, ultra-high surface area, and structural designability[1].Increasing porosity can augment the catalytic activity by increasing the surface area, thereby enhancing the ORR kinetics.In the present work, a CFZ-NPC (CoFeZn-MOF derived nanoporous carbon) was synthesized via hydrothermal method and investigated as a bifunctional catalyst for rechargeable zinc-air batteries[2]. The catalyst shows a high electrochemical activity towards oxygen reduction reaction with a half-wave potential of 830 mV vs. RHE and a comparable oxygen evolution activity (overpotential of 379 mV vs. RHE at 10 mA cm-2 ) with IrO2 (Over potential of 377 mV at 10 mA cm-2). The binder-free CFZ-NPC air electrode when applied into a Zinc-air battery system, delivers a low charge-discharge potential gap of 862 mV at 5 mA cm-2. Interestingly, the catalyst possesses an excellent electrochemical performance in the electrically rechargeable Zn-air battery over 1000 cycles at selected DOD for 157 h with a specific capacity of 890 mAh g(Zn) -1 without much efficiency drop.Financial support from Department of Science and Technology, Govt. of India under research grant number DST/TMD/MECSP/2K17/20 is gratefully acknowledged References; [1] Ren, Shuangshuang et al. 2020. “Bifunctional Electrocatalysts for Zn-Air Batteries: Recent Developments and Future Perspectives.” Journal of Materials Chemistry A 8(13): 6144–82.[2] Tang, Jing et al. 2016. “Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nano porous Carbons.” Nature Publishing Group (April): 1-8.

Plasmonic Nanostructures-Decorated ZIF-8-Derived Nanoporous Carbon for Surface-Enhanced Raman Scattering

Surface-enhanced Raman scattering (SERS) is considered to be a highly sensitive platform for chemical and biological sensing. Recently, owing to their high porosity and large surface area, metal–organic frameworks (MOFs) have attracted considerable attention in sensing applications. Porous carbon nanostructures are promising SERS substrates due to their strong broadband charge-transfer resonance and reproducible fabrication. Furthermore, an extraordinarily large enhancement of the electromagnetic field enables plasmonic nanomaterials to be ideal SERS substrates. Here, we demonstrate the porous Au@Ag nanostructure-decorated MOF-derived nanoporous carbon (NPC) for highly efficient SERS sensing. Specifically, this plasmonic nanomaterial–NPC composite offers high Raman signal enhancement with the ability to detect the model Raman reporter 2-naphthalenethiol (2-NT) at picomolar concentration levels.

MOF-derived nanoporous carbon with embedded cobalt nanoparticles as interlayer for high-performance Li–S batteries

Lithium–sulfur (Li–S) battery is one of the promising energy storage systems due to its high theoretical energy density with low cost. The main challenge at present for its commercialization is the polysulfides shuttling, leading to poor cycling performance. Here, we report a facilely prepared metal-organic framework (MOF)-derived nanoporous carbon with embedded cobalt nanoparticles (NPCo/C) for alleviating the polysulfides shuttling. The NPCo/C with large surface area and abundant Co nanoparticles is simply prepared by direct carbonization of a Co-based MOF material, which is combined with graphene to construct a robust membrane as the interlayer (NPCo/C@G) to modify the pristine separator. The NPCo/C@G-modified separator gives the battery good cycling stability (707 mAh g−1 after 300 cycles at 0.5 C) and rate performance (capacity decay rate of 0.18% in 300 cycles at 2 C). Excellent battery performance (620 mAh g−1 after 100 cycles at 0.5 C) is exhibited even under ultra-low loading of NPCo/C@G (0.08 mg cm−2). The superior electrochemical performance is mainly attributed to abundant exposed Co active sites in NPCo/C to immobilize polysulfides and accelerate sulfur redox kinetics as well as excellent electrical conductivity of NPCo/C@G for improved sulfur utilization. This study provides a guidance for designing functional separators for Li–S battery application in the near future.

A Label-Free Electrochemical Aptasensor Based on Zn/Fe Bimetallic MOF Derived Nanoporous Carbon for Ultra-Sensitive and Selective Determination of Paraquat in Vegetables.

Paraquat (PQ) has high acute toxicity, even at low concentrations. For most people, the main pathway of exposure to PQ is through the diet. Therefore, the development of simple and efficient methods for PQ testing is critical for ensuring food safety. In this study, a new electrochemical detection strategy for paraquat is proposed based on the specific binding of PQ to its nucleic acid aptamer. Firstly, the Zn/Fe bimetallic ZIF derived nanoporous carbon (Zn/Fe-ZIF-NPC) and nickel hexacyanoferrate nanoparticles (NiHCF-NPs) were sequentially modified onto the glassy carbon electrode (GCE). NiHCF-NPs served as the signal probes, while Zn/Fe-ZIF-NPC facilitated electron transfer and effectively enhanced the sensing signal of NiHCF-NPs. Au nanoparticles (AuNPs) were then electrodeposited on the NiHCF-NPs/Zn/Fe-ZIF-NPC/GCE and then the thiolated aptamer was assembled on the AuNPs/NiHCF-NPs/Zn/Fe-ZIF-NPC/GCE via Au-S bonding. When incubated with PQ, the formation of PQ–aptamer complexes delayed the interfacial electron transport reaction of NiHCF-NPs, which caused a decrease in the current signals. As a result, simple and highly sensitive detection of PQ can be readily achieved by detecting the signal changes. A linear range was obtained from 0.001 to 100 mg/L with a detection limit as low as 0.34 μg/L. Due to the recognition specificity of the aptamer to its target molecule, the proposed method has excellent anti-interference ability. The prepared electrochemical aptasensor was successfully used for PQ assay in lettuce, cabbage and agriculture irrigation water samples with recoveries ranging from 96.20% to 104.02%, demonstrating the validity and practicality of the proposed method for PQ detection in real samples.

High-yield solar-driven atmospheric water harvesting of metal-organic-framework-derived nanoporous carbon with fast-diffusion water channels.

Solar-driven, sorption-based atmospheric water harvesting (AWH) offers a cost-effective solution to freshwater scarcity in arid areas. Creating AWH devices capable of performing multiple adsorption-desorption cycles per day is crucial for increasing water production rates matching human water requirements. However, achieving rapid-cycling AWH in passive harvesters has been challenging due to sorbents' slow water adsorption-desorption dynamics. Here we report an MOF-derived nanoporous carbon, a sorbent endowed with fast sorption kinetics and excellent photothermal properties, for high-yield AWH. The optimized structure (40% adsorption sites and ~1.0 nm pore size) has superior sorption kinetics due to the minimized diffusion resistance. Moreover, the carbonaceous sorbent exhibits fast desorption kinetics enabled by efficient solar-thermal heating and high thermal conductivity. A rapid-cycling water harvester based on nanoporous carbon derived from metal-organic frameworks can produce 0.18 L kgcarbon-1 h-1 of water at 30% relative humidity under one-sun illumination. The proposed design strategy is helpful to develop high-yield, solar-driven AWH for advanced freshwater-generation systems.

Functionalized MOF-Derived Nanoporous Carbon as Compatible Nanofiller to Fabricate Defect-Free PDMS-Based Mixed Matrix Pervaporation Membranes.

Metal–organic framework (MOF)-based polydimethylsiloxane mixed matrix membranes applied for alcohol recovery with high permeability and selectivity are drawing more and more attention. However, the design and fabrication of high-quality and stable MOF-based mixed matrix membrane for pervaporation are still a big challenge. Herein, PDMS functionalized MOF-derived nanoporous carbon (P-ZNC) was first explored as compatible nanofiller to mutually blend with polydimethylsiloxane on PVDF substrate to fabricate defect-free mixed matrix membranes via dip-coating and thermal cross-linkng. Induced by UV illumination, hydrophobic modification of MOF-derived nanoporous carbon was successfully realized under mild conditions within one step, simplifying the operation step. By using this facile strategy, we can not only solve the existing problem of agglomeration, but also covalently cross-link MOF derivative with polymeric matrix and effectively eliminate the interface defect between polymer and nanoparticles without any extra steps. The method also gives a good level of generality for the synthesis of versatile stable nanoporous MOF-derived carbon-based mixed matrix membranes on various supports. The prepared PDMS/P-ZNC with commendable structures possessed excellent separation performance in low concentration n-butanol recovery and had a good balance between permeance, selectivity, and stability.

MOF-Derived Nanoporous Carbon Incorporated in the Cation Exchange Membrane for Gradient Power Generation.

Ion exchange membranes (IEMs), as a part of the reverse electrodialysis (RED) system, play an important role in salinity gradient power (SGP) generation. Structure optimization of IEMs is critical to increase the power production by RED. In this work, metal organic framework (MOF)-derived nanoporous carbons (hollow zeolitic imidazolate framework (ZIF)-derived nanoporous carbons, HZCs) were incorporated in a sulfonated poly (2, 6-dimethyl-1,4-phenylene oxide) (sPPO) membrane to prepare an organic−inorganic nanocomposite cation exchange membrane (CEM). Physicochemical properties, electrochemical properties, and power generation of the synthesized nanocomposite membranes with different HZCs loading were characterized. The results show that the incorporated HZCs could tailor the microstructure of the membrane matrix, providing a superior performance of the nanocomposite membrane. With a HZCs loading of 1.0 wt.%, the nanocomposite membrane possessed the highest permselectivity of 77.61% and the lowest area resistance of 0.42 Ω·cm2, along with a super gross power density of 0.45 W/m2, which was 87.5% (about 1.87 times) higher than that of the blank sPPO membrane. Therefore, incorporating of an appropriate amount of HZCs in the ion-exchange membrane can improve the performance of the membrane, providing a promising method to increase the power generation of the RED system.

Encapsulation and controlled release of fragrances from MIL-101(Fe)-based recyclable magnetic nanoporous carbon

In this work, MIL-101(Fe), a biocompatible metal-organic framework (MOFs), was calcinated to obtain high-performance nanoporous carbon (Fe-MNPC). The carbonized product was selected as a promising candidate adsorbent for the controlled release of fragrances. Isobutyraldehyde (BA), ethyl acetate (EA), benzaldehyde (BAD), and methoxybenzene (MB) of high saturated vapor pressures were selected as the representative fragrances for inclusion and controlled release studies. The prepared Fe-MNPC featured a large specific surface area (SSA) of 121.46 m2 g−1, which provided feasible storage and controlled-release ability. The high stability and magnetic property of Fe-MNPC guaranteed fast collection and efficient recyclability. The effective loading amounts of BA are 0.22 and EA are 0.16 g g−1, respectively, while that of BAD and MB can reach 0.56 and 0.63 g g−1, respectively. Fe-MNPC exhibited a much longer release effect over BA and EA than BAD and MB, suggesting an excellent adsorption-release selectivity of Fe-MNPC to different fragrances. This study sets an example for the usability of MOF-derived nanoporous carbon (NPC) in fragrance release and enriches the application of NPC in volatile release.

Nanoporous carbon nanowires derived from one-dimensional metal-organic framework core-shell hybrids for enhanced electrochemical energy storage

One-dimensional core-shell metal-organic framework (MOF) hybrids is expected to combine the merits of one-dimensional structure and core-shell configuration, which shows superiority to the three-dimensional counterparts and the single core or shell MOFs. However, the construction of one-dimensional MOF core-shell hybrids still remains challenging to date. In this manuscript, one-dimensional MOF core-shell heterogeneous nanowires are successfully fabricated via a solvent-assisted transformation approach. After a simple carbonization treatment, nanoporous carbon nanowires derived from the prepared MOF core-shell hybrids can be obtained, in which a nitrogen-doped carbon shell is tightly decorated on a graphite carbon core. Due to such an unique nanostructure, the core-shell MOF-derived nanoporous carbon nanowires exhibit enhanced specific capacity, rate and cycling performance for electrochemical Li+ storage in comparison to the counterparts derived from single core and shell MOFs. The present study clearly reveals the importance of MOF structural engineering.

Designing core–shell metal–organic framework hybrids: toward high-efficiency electrochemical potassium storage

Due to the unique core–shell structure which enables mutual advantage complement of the core and the shell, the electrochemical K+ storage property of core–shell MOF-derived nanoporous carbon is superior to that of single MOF-derived counterparts.

1D-3D mixed-dimensional MnO2@nanoporous carbon composites derived from Mn-metal organic framework with full-band ultra-strong microwave absorption response

Nano-porous carbon (NPC) composites derived from metal-organic frameworks (MOFs) possess effective microwave absorption (MA) properties. However, the fabrication of MOF-derived NPC composites with full-band MA performance is challenging. In this work, the effect of the bandgap on the microwave dielectric behavior of Mn-MOF derivatives was investigated. The results demonstrated that a narrower MnO2 bandgap resulted in higher conductivity and a larger dielectric constant of the corresponding materials. The three-dimensional (3D) [email protected] composites achieved excellent low-frequency MA ability. The maximum reflection loss (RL) of [email protected] carbonized at 800 °C reached −54.38 dB at 5.12 GHz. The 1D-3D mixed-dimensional MnO2@NPC composites with the ultra-strong MA response in the full band were obtained by oxidizing [email protected] to MnO2@NPC. MnO2@NPC-800 showed superior MA capacity with the maximum RL value equal to −63.21 dB at 12.48 GHz and 2.05 mm thickness. The maximum RL values in S, C, X, Ku bands also exceeded −50 dB. Such an outstanding MA performance of MnO2@NPC-800 composite was attributed to the MnO2 presence and its multi-dimensional structure. This work provides the foundation for the fabrication of MOF-derived materials capable of full-band MA.

Nanoporous Carbon Derived from MOF-5: A Superadsorbent for Copper Ions.

In this work, nanoporous carbon (NPC) was synthesized by direct carbonization of MOF-5 (a famous metal–organic framework). The structure and morphology of the prepared MOF-derived nanoporous carbon (MOF-NPC) were investigated by X-ray diffraction, N2 adsorption/desorption isotherm, Raman spectroscopy, thermogravimetric analysis, and scanning electron microscopy methods. The MOF-NPC was then used to adsorb copper ions from aqueous solutions. To evaluate the performance of the prepared MOF-NPC to remove copper ions, both adsorption kinetics and adsorption equilibrium experiments were carried out and then the obtained data were modeled with various models. Also, the efficacy of temperature and the pH of the solution on the removal efficiency were checked. The results show that the prepared MOF-NPC is a superadsorbent for the removal of copper ions from aqueous solutions. Finally, the removal percentage of copper ions by the prepared MOF-NPC was compared with other activated carbon adsorbents to show its incredible efficiency.

Enhancing enrichment ability of a nanoporous carbon based solid-phase microextraction device by a morphological modulation strategy

Recent works of designing excellent adsorbents emphasized on the specific surface areas and porosities of the materials. This study presents the influence of morphological modulation on extraction efficiencies of materials for the first time. Sea urchin-like nanoporous carbon (NPC), derived from metal organic framework (MOF), was synthesized and fabricated as solid phase microextraction (SPME) device. The morphological modulated structure of the NPC, with enhanced effective adsorption sites produced by the pointed and sharp edges, could improve the extraction efficiencies of the NPC. Comparing with the unmodulated one, NPC with morphological modulation possessed higher extraction efficiencies (2 flod) as well as accelerated sampling rates (5 flod) on benzene series compounds (BTEX), improving the sensitivity of the sampling method (limits of detection ranged from 0.08 ng L−1 to 0.36 ng L−1). Moreover, it was also the first time that the moisture sensitive MOF-derived NPC was exploited as the SPME adsorbent. In general, this study was expected to be an important advance in broadening the approaches on designing a superior SPME adsorbents not only emphasizing on the specific surface area as well as porosity but also the morphology.

High energy density asymmetric supercapacitors based on MOF-derived nanoporous carbon/manganese dioxide hybrids

Nanoporous carbon materials with high specific surface areas have attracted increasing attention for electrochemical energy storage applications. Metal organic frameworks (MOF) as a good precursor for nanoporous carbon could be used as a promising substrate to improve the energy density of the electrode because of its high specific surface area and high porosity. Here we fabricated MOF-derived nanoporous carbon (MOF-NPC) by direct calcination of zine-based MOF with different carbonization temperatures and synthesized MOF-NPC/MnO2 hybrids via a self-controlled redox process with MnO2 nanostructures well confining in the porous structures of MOF-NPC. An asymmetric supercapacitor has been developed using MOF-NPC/MnO2 hybrids as positive electrode and MOF-NPC as negative electrode in a neutral aqueous Na2SO4 electrolyte. Due to the excellent structure of MOF-NPC as a porous scaffold, optimized asymmetric device could be reversibly cycled in the voltage range of 0–2.2V, and exhibits a maximum energy density of 76.02Whkg−1 (for a power density of 2.20kWkg−1) and a maximum power density of 22.00kWkg−1 (for an energy density of 49.56Whkg−1), demonstrating its strong potential for the practical applications of energy storage devices.

Study on adsorption of copper ion from aqueous solution by MOF-derived nanoporous carbon

Nanoporous carbons (NC) materials are synthesized by direct carbonization of zeolitic imidazolate framework (ZIF-8), a well-known metal organic framework (MOF). Here we study the efficiency of the obtained MOF-derived nanoporous carbon (MOF-NC) particles as adsorbent for the removal of copper (Cu) ions from an aqueous solution. The adsorption behavior is carefully studied from both kinetic and equilibrium point of view from which the obtained data can be described with different models. The efficiency of MOF-NC for removing Cu ion is compared with other carbonaceous adsorbents. The effect of solution pH and temperature on the removal percentage is also studied.

MOF-derived Nanoporous Carbon as Intracellular Drug Delivery Carriers

Precursory Research for Embryon icSc ence and Technology (PRESTO), Japan Sc ogy Agency (JST),4-1-8 Honcho, Kawaguchi,Saitama 332-0012(E-mail: kevinwu@nims.go.jp, Yamauchi.Yusuke@nims.go.jp)We prepared nanoporous carbon (NC) particles of approx-imately 50-nm diameter by direct carbonization of metal­organic frameworks (MOFs). The obtained MOF-derived NC(MOF-NC) particles exhibit very high biocompatibility and,hence, are promising as intracellular drug delivery carriers.Many drug carriers, such as dendrimers, micelles, emul-sions, organic­inorganic hybrids, nanoparticles, nanotubes, lip-osomes, metal­organic frameworks (MOFs), and hydrogels,have been proposed so far.