MOF-derived Porous Carbon Research Articles

Metal-organic framework-derived silver/copper-oxide catalyst for boosting the productivity of carbon dioxide electrocatalysis to ethylene

Electrochemical reduction of CO2 into valuable multi-carbon (C2) chemicals holds promise for mitigating CO2 emissions and enabling artificial carbon cycling. However, achieving high selectivity remains challenging due to the limited activity and active sites of CC coupling catalysts. Herein, we report an Ag-modified Cu-oxide catalyst (CuO/Ag@C) derived from metal-organic frameworks (MOF), capable of efficiently converting CO2 to C2H4. The MOF-derived porous carbon confines the size of metal nanoparticles, ensuring sufficient exposure of active sites. Remarkably, the CuO/Ag@C catalyst achieves an impressive Faradaic efficiency of 48.6% for C2H4 at −0.7 V vs. RHE, demonstrating excellent stability. Both experimental results and theoretical calculations indicate that Ag sites promote the production of CO, enhancing the coverage of *CO on Cu sites. Furthermore, the reconfiguration of charge density at the Cu-Ag interface optimizes the electronic states of the reaction sites, reducing the formation energy of the key intermediate *OCCHO, thereby favoring C2H4 production effectively. This work provides insight into structurally rational catalyst design for highly active and selective multiphase catalysts.

MOF-Derived Zn/N-Doped Porous Carbon Film on a Carbon Nanotube for High-Performance Supercapacitors.

Designing high-performance binder-free electrochemical electrodes is crucially important toward supercapacitors. In this paper, a Zn/N-doped porous carbon film coating on flexible carbon nanotubes (ZIF-8@CT-800) derived from the epitaxial Zn-MOF film growth on cotton textile was successfully fabricated via a combination of the liquid-phase epitaxial (LPE) method and calcination treatments. The ZIF-8@CT-800 serves directly as a self-supported electrode for supercapacitors and exhibits a high areal capacitance of 930 mF·cm-2 at a current density of 1 mA·cm-2 and a good recyclability of 86% after 2000 cycles. The excellent supercapacitor property is ascribed to the unique structural design of ZIF-8@CT-800, which provides appropriate channels for enhanced electronic and ionic transport as well as increased surface area for accessing more electrolyte ions. This work will provide significant guidance for designing MOF-derived porous carbon to construct flexible binder-free electrode materials with high electrochemical performance.

Metal-organic framework-derived porous carbon for the advanced aqueous zinc-ion hybrid capacitor

Metal-organic framework-derived porous carbon for the advanced aqueous zinc-ion hybrid capacitor

Spinel Nickel Ferrite on Metal–Organic Framework-Derived Porous Carbon as a Robust Faradaic Electrode for Enhanced Flow Capacitive Deionization

Spinel Nickel Ferrite on Metal–Organic Framework-Derived Porous Carbon as a Robust Faradaic Electrode for Enhanced Flow Capacitive Deionization

Electrochemical aptasensors based on porous carbon derived from graphene oxide/ZIF-8 composites for the detection of Erwinia cypripedii

In this research, self-screening aptamer and MOFs-derived nanomaterial have been combined to construct electrochemical aptasensor for environmental detection. By utilizing the large specific surface area of reduced graphene oxide (rGO), ZIF-8 was grown in situ on surface of rGO, and the composites was pyrolyzed to obtain MOFs-derived porous carbon materials (rGO-NCZIF). Thanks to the synergistic effect between rGO and NCZIF, the complex exhibits remarkable characteristics, including a high electron transfer rate and electrocatalytic activity. In addition, the orderly arrangement of imidazole ligands within ZIF-8 facilitated the uniform doping of nitrogen elements into the porous carbon, thereby significantly enhancing its electrochemical performance. After carboxylation, rGO-NCZIF was functionalized with self-screening aptamer for fabricating electrochemical aptasensor, which can be used to detect Erwinia cypripedii, a kind of quarantine plant bacteria, with detection limit of 4.92 × 103 cfu/mL. Due to the simplicity and speed, the aptasensor is suitable for rapid customs inspection and quarantine. Additionally, the universality of this sensing strategy was verified through exosomes detection by changing the aptamer. The results indicated that the rGO-NCZIF-based electrochemical aptasensor had practical value in the environmental and medical fields.

MOF-derived porous carbon microspheres Ni@C-acid as solid-phase microextraction coating for extraction of polycyclic aromatic hydrocarbons from tea infusions

The improvement of the stability and adsorption properties of materials on targets in sample pre-treatment has long been an objective. Extensive efforts have been made to achieve this goal. In this work, metal-organic framework Ni-MOF precursors were first synthesized by solvothermal method using polyvinylpyrrolidone (PVP) as an ideal templating agent, stabiliser and nanoparticle dispersant. After carbonization and acid washing, the nanoporous carbon microspheres material (Ni@C-acid) was obtained. Compared with the material without acid treatment (Ni@C), the specific surface area, pore volume, adsorption performance of Ni@C-acid were increased. Thanks to its excellent characteristics (high stability, abundant benzene rings), Ni@C-acid was used as fiber coatings in headspace solid-phase microextraction (HS-SPME) technology for extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The experimental parameters of extraction temperature, extraction time, agitation speed, desorption temperature, desorption time and sodium chloride (NaCl) concentration were studied. Under optimal experimental conditions, the wide linear range (0.01-30 ng mL−1), the good correlation coefficient (0.9916-0.9984), the low detection limit (0.003-0.011 ng mL−1), and the high enrichment factor (5273-13793) were obtained. The established method was successfully used for the detection of trace PAHs in actual tea infusions samples and satisfied recoveries ranging from 80.94-118.62 % were achieved. The present work provides a simple method for the preparation of highly stable and adsorbable porous carbon microsphere materials with potential applications in the extraction of environmental pollutants.

Diatomite supported highly-dispersed ZnO/Zn-co-embedded ZIF-8 derived porous carbon composites for adsorption desulfurization

The metal organic framework (MOFs)-derived porous carbon materials with highly dispersed metal active sites were of the exclusive application foreground in many field, such as catalyst, electrochemistry, adsorption desulfurization and so on. However, the loss issue of metal active sites in MOFs frame was indispensable during the high temperature carbonization because of the lower boiling point of many metals, thus fundamentally affecting the atom-scale uniform distribution merit of MOFs-derived porous carbon materials. This work was to provide a novel strategy to address the loss issue of the active metal volatilization in the fabrication of MOFs-derived porous carbon materials. The ZnO nanosheets were pre-grown on the surface of diatomite by using in-situ microwave-assisted preparation, and thereafter the Zn-containing ZIF-8 particles covered the surface of ZnO nanosheets by virtue of the ZnO-induced growth. The results affirmed that the high content Zn-doped porous carbon materials were achieved and the Zn volatilization in MOFs was restrained on account of the occurrence of ZnO on diatomite (DE) surface during the carbonization. The adsorption desulfurization performance of the ZnO/Zn-embedded porous carbon materials/DE (ZnO/Zn/C@DE) was examined by the sulfur-containing compounds in simulated oil. The adsorption desulfurization performance investigation indicated that the ZnO/Zn/C@DE had the optimum adsorption capacities of 45.3 mg/g for benzothiophene and 37.4 mg/g for thiophene. Nonetheless, the competitive adsorption desulfurization finding of toluene in simulated oil showed that the adsorption capacities of ZnO/Zn/C@DE for TH and BT were dramatically descended, suggesting the presence of S-M interaction, wherein S stood for the S atom in a thiophene molecule and their analogs, and M for Zn atoms in porous carbon materials.

P507-modified magnetic porous carbon derived from metal-organic frameworks for efficient separation of zirconium(IV) and hafnium(IV)

Extractant-based solid phase extraction exhibit practical application potential for efficient separation of Zr(IV) and Hf(IV), where the key is to regulate the host–guest interaction between the guest extraction agents and the host matrices to obtain high performance. However, the current research on the host matrices of extraction agents is insufficient. Leveraging the tunability of metal–organic frameworks (MOFs), we successfully prepared a magnetic MOF-derived porous carbon (C(Zn/Co-ZIF)) with a high specific surface area and Co-Nx active sites as an excellent matrix. This was achieved by deliberately controlling the pore volume and microenvironment through a mixed precursor strategy and high-temperature pyrolysis method. Furthermore, as an excellent extractant for the separation of Zr(IV) and Hf(IV) in solvent extraction, 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester (P507) was carefully selected to modify C(Zn/Co-ZIF) to obtain C(Zn/Co-ZIF)@P507 by impregnation. Impressively, the maximum adsorption capacities of C(Zn/Co-ZIF)@P507 for Zr(IV) and Hf(IV) were up to be 0.58 and 0.39 mmol/g, respectively, while exhibiting excellent separation coefficient. Further mechanism studies indicated that the combination of high specific surface area and abundant Co-Nx active sites of C(Zn/Co-ZIF) leaded to strong interaction with P507, resulting in the excellent adsorption and separation performance of Zr(IV) and Hf(IV) based on the coordination between phosphinic groups of P507 and Zr(IV)/Hf(IV).

A robust bioplatform based on DNA-gated nanoscale porous carbon derived from a metal-organic framework for specific detection of Herpes simplex virus type 1

In this study, a highly efficient sensing platform based on metal-organic framework-derived porous carbon (MOF-PC) and bio-gatekeeper strategy was designed for the sensitive detection of Herpes simplex virus type 1 (HSV-1). To realize the aim above, MOF-PC was obtained through the carbonization of the zeolitic imidazolate framework (ZIF-8). The electroactive dye methylene blue (MB) was then captured as a signal probe in the MOF-PC pores. Specifically, HSV-1 highly specific antisense ssDNA oligonucleotide was connected to MOF-PC through π-stacking interaction as a gatekeeper and sealed up the pores of MOF-PC. By adding the targets (synthetic ssDNA target or total genome HSV-1 DNA) and hybridization between the immobilized specific antisense ssDNA oligonucleotides and the targets, the double-stranded DNA (dsDNA) was separated from the MOF-PC surface due to the low affinity of the MOF-PC to the dsDNA. Meanwhile, MBs were released from the opened holes of MOF-PC. Therefore, the intensity of MB peak current in the absence of a target was high and then decreased by releasing and washing of MB molecules. The MB@MOF-PC responded linearly to synthetic ssDNA target in the range from 10−18 to 10−8 M and isolated total genome HSV-1 DNA in the range from 102 to 108 copies/mL. The detection limits of 0.79 aM and 83.4 copies/mL were obtained for the synthetic ssDNA target and total genome HSV-1 DNA, respectively.

ZIF-derived porous carbon loaded multicomponent heterostructured yolk@shell nanospheres as an ultrasensitive electrochemical sensing platform for the detection of caffeic acid in food

Multicomponent heterogeneous structures of yolk@shell nanospheres embedded in MOF-derived porous carbon are potentially excellent electrocatalytic materials. In this work, the multicomponent yolk@shell nanospheres (Au@Co3O4@CeO2) were synthesized through an autocatalytic redox reaction. The synergistic and interfacial effects between Co3O4 and CeO2 can expose more active sites and enhance the catalytic activity. Then, the electrical conductivity of Au@Co3O4@CeO2 was improved using N-doped carbon nanomaterials (NPC), which was derived from ZIF-8 by high-temperature pyrolysis. The synergistic catalytic effect between ZIF-8 derived NPC and Au@Co3O4@CeO2 resulted in the highest electrochemical response current to caffeic acid in this composite. Under optimal conditions, the prepared modified electrode showed a LOD (limit of detection) of 5.7 × 10−10 M for CA and a linear range of 1.0 × 10−9 to 3.0 × 10−6 M. Meanwhile, it showed remarkable selectivity for CA in the anti-interference experiments and can be applied to the detection in food samples (strawberry and red wine). This work has developed a novel sensing material for sensitive detection of CA, broadening the application of multi-component shell-core structured metal oxidation.

Synergistic interaction of in situ S,N-codoping-mediated non-radical pathway for highly active and robust water decontamination

Metal-organic frameworks (MOFs)-derived heteroatom-doped carbon-based catalysts are commonly used in sewage treatment. However, the challenge lies in developing a simple route for heteroatom co-doping of MOFs-derived porous carbon that efficiently degrades organic pollutants without the need for additional post-treatment procedures. Herein, built-in Co nanoparticles are integrated with S,N-codoped porous carbon through a straightforward in situ co-doping strategy using ZnS nanoparticles as templates and a sulfur source. This approach simplifies the process of achieving S,N-codoping of zeolitic imidazolate frameworks-derived carbon without requiring extra nitrogen and sulfur sources or post-treatment procedures. The resulting Co@SNPC-900 catalyst demonstrates high catalytic performance in degrading tetracycline (TC) via peroxymonosulfate (PMS) activation, showing a removal efficiency of 97% in 30 min and excellent cycling stability. Furthermore, the Co@SNPC-900/PMS system shows strong resistance to changes in solution pH, interference from inorganic ions, and humic acid. The synergistic effects between S and N co-doping contribute to the formation of dominant non-radical pathways for boosting TC degradation. The study also elucidates three reaction pathways and identifies including sixteen intermediates with lower toxicity. This research presents a straightforward in situ co-doping strategy for producing highly active and durable built-in metal nanoparticles integrated porous carbon catalysts for environmental remediation.

Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 μg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 μg/L and 0.03-0.42 μg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 μg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

MOF-derived porous graphitic carbon with optimized plateau capacity and rate capability for high performance lithium-ion capacitors

MOF-derived porous graphitic carbon with optimized plateau capacity and rate capability for high performance lithium-ion capacitors

Ultrasensitive electrochemical sensing of catechol and hydroquinone via single-atom nanozyme anchored on MOF-derived porous carbon

Single-atom nanozymes (SANs) can significantly enhance the sensitivity and selectivity of electrochemical sensing platforms due to the homogeneity of their active sites, full atom utilization, and high catalytic activity. In this study, we demonstrate the synthesis and characterization of a high-density Co-based single-atom nanozyme anchored on activated MOF-derived porous carbon (Co-AcNC-3) via a cascade anchoring strategy for ultrasensitive, simultaneous electrochemical detection of catechol (CC) and hydroquinone (HQ). The Co-AcNC-3 displays a large specific surface area, high defectivity, and abundant oxygen-containing groups, with Co atoms being atomically dispersed throughout the carbon support via Co–N bonds. The Co-AcNC-3 biosensor exhibits superior electrochemical signals for CC and HQ, with linear ranges of 4.0 μM–300.0 μM. and detection limits of 0.072 μM and 0.034 μM, respectively. Moreover, the Co-AcNC-3 biosensor has shown excellent performance in accurately detecting CC and HQ in actual samples. Our findings highlight the potential of the proposed Co-AcNC-3 biosensor as a reliable and promising sensing platform for determining CC and HQ.

Edge defects-regulated FeCo metalic sites confined in N-doped carbon polyhedron as an efficient ORR catalyst for durable Zn-air battery

Metal sites or nanoparticles immobilized on MOF-derived porous carbon matrix have gained enormous attention for oxygen electroreduction reaction (ORR), but they still suffered from the insufficient catalytic performance. Herein, we introduced edge defects to regulate the ORR performance of N-doped carbon polyhedron-supported FeCo bimetallic catalysts via a facile NaCl/KCl-assisted pyrolysis. HR-TEM, HAADF-STEM, Raman spectra, XPS and EPR analysis confirmed the existence of uniform FeCo atoms and edge defects within N-doped porous carbon polyhedrons and their mutual effect helped promoting ORR performance. The resulting FeCo-NC-30 exhibited more excellent ORR activity with E1/2 of 0.86 V, and faster kinetic process with a higher kinetic current density, Jk,E = 0.85V = 7.15 mA/cm2. As a cathode catalyst, it delivered a desirable power density of 196.9 mW/cm2, comparable to Pt/C, in home-made Zn-air batteries. Our findings demonstrated that the electronic tuning effect caused by carbon edge defects and synergistic bimetallic interactions is beneficial for enhancing ORR activity.

Hollow Core–Shell Metal–Organic Framework-Derived Porous Carbon Hybrid for Electrochemical Na+ Storage

Hollow Core–Shell Metal–Organic Framework-Derived Porous Carbon Hybrid for Electrochemical Na⁺ Storage

Polydopamine-modified MOF-5-derived carbon as persulfate activator for aniline aerofloat degradation

Residual flotation chemicals in beneficiation wastewater seriously threaten local ecosystems, such as groundwater or soil, and must be treated effectively. Currently, the degradation of organic pollutants using nitrided MOFs-derived carbon to activate persulfate (PDS) has attracted considerable attention. Hence, we developed a new synthetic strategy to load dopamine hydrochloride (PDA) onto MOF-5-derived porous carbon (PC) to form NPC, and the degradation of a typical flotation Aniline aerofloat (AAF) at high salinity by a low dose of the NPC/PDS system was investigated. Several characterization analyses such as TEM, XRD, Raman, FT-IR and XPS demonstrated that the nitrogen-rich indolequinone unit in PDA provided nitrogen to PC during the pyrolysis process. This enabled the core-shell structure of NPC and the synergy among the multiple components to induce the AAF degradation by PDS over a wide pH scale in a short period of time. It was deduced that the degradation of AAF by the NPC-8/PDS system was a non-radical pathway dominated by 1O2, which relied mainly on the conversion of superoxide radicals (O2•−) and surface-bound radicals. Among them, the pyridine N in the sp2 hybrid carbon was considered as a possible active site. This non-radical pathway was resistant to pH changes and background substances in the water, and well overcame the inhibition of the reaction by natural organic substances and inorganic anions in natural water. In this study, A novel approach to the synthesis of homogeneous MOFs nuclear-derived porous carbon was proposed and the application of MOFs-derived porous carbon for AAF remediation of mineral processing wastewater was broadened.

α-MnO2 composite with gold nanoparticles on carbon cloth modified with MOFs-derived porous carbon for flexible and activity-enhanced sodium-ion supercapacitors

Improving the catalytic activity of electrodes in a limited space is crucial to energy storage devices such as supercapacitors. Herein, the surface activity of the flexible electrode (Au-MnO2/CPCN@CC) is enhanced by combining gold particles (AuNPs) modified α-MnO2 with conductive porous carbon nanoflakes (CPCN) derived from the metal-organic framework (MOF) on carbon cloth (CC). The Au-MnO2/CPCN@CC electrode exhibits a higher specific capacity of 503.7 F/g at 0.125 mA/cm2 and retains 87.68% capacity after 10,000 cycles in 1 M Na2SO4, while the structure without AuNPs achieves 242.6 F/g and 61.07% capacity retention after 10,000 cycles. The high stability of Au-MnO2/CPCN@CC stems from the good pseudocapacitance ratio of 83.80% at 1 mV/s compared to 78.43% of MnO2/CPCN@CC and 40.88% of Au/CPCN@CC. The supercapacitor assembled with Au-MnO2/CPCN@CC as the positive electrode and activated carbon (AC) as the negative electrode in 1 M NaPF6 shows an excellent power density of 79.96 W/kg at 71.48 Wh/kg as well as 81.93% capacitance retention after 10,000 cycles. Density-functional theory (DFT) calculations of Au-MnO2/CPCN composite reveal a sodium-ion adsorption energy of 3.744 eV and a large DOS near Fermi level. Hence, Au nanoparticles (AuNPs) and MOFs-derived CPCN lead to enhanced surface electron transport of MnO2 and ultimately superior performance.

MOF-derived porous carbon nanozyme-based flexible electrochemical sensing system for in situ and real-time monitoring of H2O2 released from cells

A novel flexible electrochemical sensor based on porous carbon nanosheets (PCNSs) nanozyme has been constructed for in situ and real-time monitoring of H2O2 released by cells. The PCNSs are prepared with the integration of thermal transformation, thermal activation and sonochemical exfoliation by using zeolitic imidazolate frameworks as template. The PCNSs exhibit high electrical conductivity, electrochemical activity and peroxidase-like catalytic properties, which is beneficial to H2O2 assay. With the transfer printing method, the flexible electrochemical sensor is obtained, which has excellent performances for H2O2 electrochemical detecting with wide linear range from 1 μM to 20 mM and a low detection limit of 0.76 μM. Owing to the great biocompatibility, the flexible sensor guarantees the growth of living cells for 72 h and realizes in situ and real-time monitoring the release of H2O2 from HeLa cells. The strategy of porous nanozyme preparation and flexible sensor construction provided a promising way for in situ and real-time assay of small molecules in the cellular microenvironment.

MOF-derived Porous Carbon Nanofiber Assembly as High Efficiency ORR Electrocatalysts for Zinc-air Batteries

MOF-derived Porous Carbon Nanofiber Assembly as High Efficiency ORR Electrocatalysts for Zinc-air Batteries