RESUMO
The highly dispersed small-size metal co-catalysts can effectively improve the photocatalytic efficiency of semiconductor photocatalysts by separating photogenerated electrons and enriching active sites. However, this system tends to aggregate in the absence of carrier, resulting in the decrease of active sites. Here, MOF-derived carbon skeleton (MDCS) encapsulated Ni nanoparticles (Ni@MDCS) and BiOBr was loaded onto carbonized cellulose fibers (CCF) with the help of polydopamine (PDA) to construct high-performance and recyclable photocatalytic paper for photocatalytic degradation of organic dyes in water. The characterization results showed that MDCS promoted good dispersion of Ni nanoparticles and provided sufficient active sites. And Ni@MDCS as a co-catalyst accelerated the separation of photogenerated carriers in BiOBr. The PDA improved the loading state of Ni@MDCS on CCF and converted into N-doped C in the carbonization process for further increasing the transfer efficiency of photogenerated electrons. In the composite paper, the stable loading of Ni@MDCS/BiOBr hybrid on CCF improved the dispersion and reusability of photocatalyst. The degradation rate of rhodamine B on CCF/PDA-C/Ni@MDCS/BiOBr paper was as high as 94.6 % after 60 min visible light irradiation, which was about 2.5 times higher than that of CCF/BiOBr paper. During 10 cycles, CCF/PDA-C/Ni@MDCS/BiOBr paper maintained high photocatalytic efficiency and good structural stability. This study provides a new way for developing high-performance and recyclable photocatalytic paper.
RESUMO
BACKGROUND: Transition metal phosphides with properties similar to platinum metal have received increasing attention for the non-enzymatic detection of glucose. However, the requirement of highly corrosive reagent during sample pretreatment would impose a potential risk to the human body, limiting their practical applications. RESULTS: In this study, we report a self-powered microfluidic device for the non-enzymatic detection of glucose using nickel phosphide (Ni2P) hybrid as the catalyst. The Ni2P hybrid is synthesized by pyrolysis of metal-organic framework (MOF)-based precursor and in-situ phosphating process, showing two linear detection ranges (1 µM-1 mM, 1 mM-6 mM) toward glucose with the detection limit of 0.32 µM. The good performance of Ni2P hybrid for glucose is attributed to the synergistic effect of Ni2P active sites and N-doped porous carbon matrix. The microchip is integrated with a NaOH-loaded paper pad and a capillary-based micropump, enabling the automatic NaOH redissolution and delivery of sample solution into the detection chamber. Under the optimized condition, the Ni2P hybrid-based microchip realized the detection of glucose in a user-friendly way. Besides, the feasibility of using this microchip for glucose detection in real serum samples has also been validated. SIGNIFICANCE: This article presents a facile fabrication method utilizing a MOF template to synthesize a Ni2P hybrid catalyst. By leveraging the synergy between the Ni2P active sites and the N-doped carbon matrix, an exceptional electrochemical detection performance for glucose has been achieved. Additionally, a self-powered chip device has been developed for convenient glucose detection based on the pre-established high pH environment on the chip.
Assuntos
Técnicas Eletroquímicas , Eletrodos , Níquel , Níquel/química , Técnicas Eletroquímicas/instrumentação , Humanos , Glucose/análise , Fosfinas/química , Estruturas Metalorgânicas/química , Limite de Detecção , Dispositivos Lab-On-A-Chip , Glicemia/análise , CatáliseRESUMO
Due to their facile tunability, metal-organic frameworks (MOFs) are employed as precursors and templates to construct advanced functional materials with unique and desired chemical, physical, mechanical, and morphological properties. By tuning MOF precursor composition and manipulating conversion processes, various MOF-derived materials commonly known as MOF derivatives can be constructed. The possibility of controlled and predictable properties makes MOF derivatives a preferred choice for numerous advanced technological applications. The innovative synthetic designs besides the plethora of interdisciplinary characterization approaches applicable to MOF derivatives provide the opportunity to perform a myriad of experiments to explore the performance and offer key insight to develop the next generation of advanced materials. Though there are many published works of literature describing various synthesis and characterization techniques of MOF derivatives, it is still not clear how the synthesis mechanism works and what are the best techniques to characterize these materials to probe their properties accurately. In this review, the recent development in synthesis techniques and mechanisms for a variety of MOF derivates such as MOF-derived metal oxides, porous carbon, composites/hybrids, and sulfides is summarized. Furthermore, the details of characterization techniques and fundamental working principles are summarized to probe the structural, mechanical, physiochemical, electrochemical, and electronic properties of MOF and MOF derivatives. The future trends and some remaining challenges in the synthesis and characterization of MOF derivatives are also discussed.
RESUMO
Metal-organic framework materials (MOFs) and their derivatives have been widely used in the field of photocatalytic water decomposition for hydrogen production. In this study, NiS/CdS was initially acquired and subsequently combined with DUT-67 via ultrasound to create a unique ternary photocatalyst NiS/CdS@DUT-67. The rate of hydrogen production for NiS/CdS@DUT-67 is 9618 µmol·g NiS/CdS-1·h-1 for NiS/CdS@DUT-67, which is 32 times and 2.5 times higher than that for CdS and NiS/CdS, respectively. Of particular interest is the fact that even after 50 h of photocatalysis, the hydrogen production rate did not show a significant decrease, demonstrating its excellent stability compared to CdS and NiS/CdS. In this ternary system, NiS and DUT-67 function as dual co-catalysts for CdS, collaborating to enhance charge separation during the photocatalysis. This study presents a clear demonstration of the advantages of utilizing metal-organic framework derivatives (MOF-derivatives) cophotocatalysts and their synergistic effect, resulting in improved photocatalytic activity and stability of semiconductors. This innovative approach provides a new perspective on constructing photocatalytic materials with exceptional performance.
RESUMO
As the most widely used metal material in supercapacitors, manganese (Mn)-based materials possess the merits of high theoretical capacitance, stable structure as well as environmental friendliness. However, due to poor conductivity and easy accumulation, the practical capacitance of Mn-based materials is far lower than that of theoretical value. Therefore, accurate structural adjustment and controllable strategies are urgently needed to optimize the electrochemical properties of Mn-based materials. Metal-organic frameworks (MOFs) are porous materials with high specific surface area (SSA), tunable pore size, and controllable structure. These features make them attractive as precursors or scaffold for the synthesis of metal-based materials and composites, which are important for electrochemical energy storage applications. Therefore, a timely and comprehensive review on the classification, design, preparation and application of Mn-based MOFs and their derivatives for supercapacitors has been given in this paper. The recent advancement of Mn-based MOFs and their derivatives applied in supercapacitor electrodes are particularly highlighted. Finally, the challenges faced by Mn-MOFs and their derivatives for supercapacitors are summarized, and strategies to further improve their performance are proposed. The aspiration is that this review will serve as a beneficial compass, guiding the logical creation of Mn-based MOFs and their derivatives in the future.
RESUMO
Laser conversion of metal-organic frameworks (MOFs) has recently emerged as a fast and low-energy consumptive approach to create scalable MOF derivatives for catalysis, energy, and optics. However, due to the virtually unlimited MOF structures and tunable laser parameters, the results of their interaction are unpredictable and poorly controlled. Here, we experimentally base a general approach to create nano- to centimeter-scale MOF derivatives with the desired nonlinear optical and catalytic properties. Five three- and two-dimensional MOFs, differing in chemical composition, topology, and thermal resistance, have been selected as precursors. Tuning the laser parameters (i.e., pulse duration from fs to ns and repetition rate from kHz to MHz), we switch between ultrafast nonthermal destruction and thermal decomposition of MOFs. We have established that regardless of the chemical composition and MOF topology, the tuning of the laser parameters allows obtaining a series of structurally different derivatives, and the transition from femtosecond to nanosecond laser regimes ensures the scaling of the derivatives from nano- to centimeter scales. Herein, the thermal resistance of MOFs affects the structure and chemical composition of the resulting derivatives. Finally, we outline the "laser parameters versus MOF structure" space, in which one can create the desired and scalable platforms with nonlinear optical properties from photoluminescence to light control and enhanced catalytic activity.
RESUMO
It remains a great challenge to properly design and synthesize single-component artificial tandem enzymes for specific substrates with high selectivity. Herein, V-MOF is synthesized by solvothermal method and its derivatives are constructed via pyrolyzing V-MOF in nitrogen atmosphere at different temperatures, which are denoted as V-MOF-y (y = 300, 400, 500, 700 and 800). V-MOF and V-MOF-y possess tandem enzyme-like activity, i.e. cholesterol oxidase-like and peroxidase-like activity. Among them, V-MOF-700 shows the strongest tandem enzyme activity for V-N bonds. Based on the cascade enzyme activity of V-MOF-700, the nonenzymatic detection platform for cholesterol by fluorescent assay can be established in the presence of o-phenylenediamine (OPD) for the first time. The detection mechanism is that V-MOF-700 catalyzes cholesterol to generate hydrogen peroxide and further form hydroxyl radical (â¢OH), which can oxidize OPD to obtain oxidized OPD (oxOPD) with yellow fluorescence. The linear detection of cholesterol ranges of 2-70 µM and 70-160 µM with a lower detection limit of 0.38 µM (S/N = 3) are obtained. This method is used to detect cholesterol in human serum successfully. Especially, it can be applied to the rough quantification of membrane cholesterol in living tumor cells, indicating that it has the potential for clinical application.
Assuntos
Técnicas Biossensoriais , Estruturas Metalorgânicas , Humanos , Estruturas Metalorgânicas/química , Peróxido de Hidrogênio/química , Fenilenodiaminas , Técnicas Biossensoriais/métodos , Limite de DetecçãoRESUMO
Metal-organic frameworks (MOFs) are crystalline materials with permanent pores constructed by the self-assembly of organic ligands and metal clusters through coordination bonds. Due to their diversity and tunability, MOFs are used as precursors to be converted into other types of functional materials by pyrolytic recrystallization. Laser-induced synthesis is proven to be a powerful pyrolytic processing technique with fast and accurate laser irradiation, low loss, high efficiency, selectivity, and programmability, which endow MOF derivatives with new features. Laser-induced MOF derivatives exhibit high versatility in multidisciplinary research fields. In this review, first, the basic principles of laser smelting and the types of materials for laser preparation of MOF derivatives are briefly introduced. Subsequently, it is focused on the peculiarity of the engineering of structural defects and their applications in catalysis, environmental protection, and energy fields. Finally, the challenges and opportunities at the current stage are highlighted with the aim of elucidating the future direction of the rapidly growing field of laser-induced synthesis of MOF derivatives.
RESUMO
Aqueous zinc-ion batteries (AZIBs) are promising for large-scale energy storage systems due to their high safety, large capacity, cost-effectiveness, and environmental friendliness. However, their commercialization is currently hindered by several challenging issues, including cathode degradation and zinc dendrite growth. Recently, metal-organic frameworks (MOFs) and their derivatives have gained significant attention and are widely used in AZIBs due to their highly porous structures, large specific surface area, and ability to design frameworks for Zn2+ shuttle. Based on preceding contributions, this review aims to generalize two design principles for MOF-based materials in AZIBs: cathode preparation and anode protection. For cathode preparation, we mainly introduce novel MOF-based electrode materials such as pure MOFs, porous carbon materials, metal oxides, and their compounds, focusing on the analysis of the specific capacity of AZIBs. For anode protection, we systematically analyze MOF-based materials used as 3D Zn architecture, solid electrolyte interfaces, novel separators, and solid-state electrolytes, highlighting the improvement in the cyclic stability of Zn anodes. Finally, we propose the future development of MOF-based materials in AZIBs. Our work can give some clues for raising the practical application level of aqueous ZIBs.
Assuntos
Estruturas Metalorgânicas , Zinco , Íons , Óxidos , CarbonoRESUMO
Excess CO2 can be effectively converted into valuable fuels and chemicals by electrochemical CO2 reduction, which can help establish a low-carbon emission economy and solve the current energy crisis. In recent years, metal-organic frameworks (MOFs), as an emerging multifunctional material with porous structure, high chemical tunability and large specific surface area, has received increasing attention in the field of electrochemical CO2 RR. In this paper, we present a comprehensive overview of various MOFs and their derivatives as CO2 RR electrocatalysts and analyze their roles in the catalytic process from physical and chemical aspects. In addition, combining experiments and theory, this article also offers a personal view on the electronic structure modulation strategies to improve electrocatalytic performance. The article concludes with an analysis of the challenges in realizing MOFs and their derivatives for electrocatalytic CO2 RR applications.
Assuntos
Dióxido de Carbono , Estruturas Metalorgânicas , Catálise , PorosidadeRESUMO
The emission of harmful gases has seriously exceeded relative standards with the rapid development of modern industry, which has shown various negative impacts on human health and the natural environment. Recently, metal-organic frameworks (MOFs)-based materials have been widely used as chemiresistive gas sensing materials for the sensitive detection and monitoring of harmful gases such as NOx, H2S, and many volatile organic compounds (VOCs). In particular, the derivatives of MOFs, which are usually semiconducting metal oxides and oxide-carbon composites, hold great potential to prompt the surface reactions with analytes and thus output amplified resistance changing signals of the chemiresistors, due to their high specific surface areas, versatile structural tunability, diversified surface architectures, as well as their superior selectivity. In this review, we introduce the recent progress in applying sophisticated MOFs-derived materials for chemiresistive gas sensors, with specific emphasis placed on the synthesis and structural regulation of the MOF derivatives, and the promoted surface reaction mechanisms between MOF derivatives and gas analytes. Furthermore, the practical application of MOF derivatives for chemiresistive sensing of NO2, H2S, and typical VOCs (e.g., acetone and ethanol) has been discussed in detail.
Assuntos
Estruturas Metalorgânicas , Compostos Orgânicos Voláteis , Humanos , Acetona , Meio Ambiente , Etanol , Gases , ÓxidosRESUMO
Metal-organic frameworks (MOFs) have been important electrochemical energy storage (EES) materials because of their rich species, large specific surface area, high porosity and rich active sites. Nevertheless, the poor conductivity, low mechanical and electrochemical stability of pristine MOFs have hindered their further applications. Although single component MOF derivatives have higher conductivity, self-aggregation often occurs during preparation. Composite design can overcome the shortcomings of MOFs and derivatives and create synergistic effects, resulting in improved electrochemical properties for EES. In this review, recent applications of MOF composites and derivatives as electrodes in different types of batteries and supercapacitors are critically discussed. The advantages, challenges, and future perspectives of MOF composites and derivatives have been given. This review may guide the development of high-performance MOF composites and derivatives in the field of EES.
Assuntos
Estruturas Metalorgânicas , Condutividade Elétrica , Fontes de Energia Elétrica , Eletrodos , PorosidadeRESUMO
It has been rarely reported the morphological control of derivatives of metal-organic frameworks (MOFs) in hydrothermal conditions for photocatalytic applications. We report here a family of highly efficient composite photocatalysts composed of terephthalic acid/terephthalate (TPA) ligand and TiO2 with various morphologies (e. g., nanoparticles, nanosheets, and nanorods). The composites are synthesized by a simple one-step hydrothermal method in various solvents (i. e., H2 O, HF, H2 SO4 , HCl, and HNO3 ) using Ti-based MOF (MIL-125(Ti)) as precursor. The formation mechanism of composite materials with different morphological features is discussed. Impressively, the composite of TiO2 nanoparticles/TPA synthesized using H2 O as solvent under hydrothermal condition exhibits the highest photocatalytic H2 activity among the studied materials, with a photocatalytic H2 production rate of 6.38â mmol g-1 h-1 , which is approximately 7.5-fold higher than pure TiO2 (Degussa, P25) and prominent apparent quantum efficiency (AQE) of 65 % at 365â nm. Furthermore, the mechanism of boosted photocatalytic H2 production is discussed.
RESUMO
Frequent petrochemical spill accidents and secondary fire hazards have threatened the ecological environment and environmental safety. The traditional purification technology has the problems of high energy consumption and secondary pollution, which also brings new challenges to spill disposal. Herein, we demonstrate a biomimetic structure-based flame-retardant polyurethane (PU) sponge (FPUF@MOF-LDH@HDTMS) for continuous oil-water separation. Inspired by desert beetle and lotus leaf, the biomimetic micro-nano composite structure was constructed by in-situ growth of metal-organic framework-derived layered double hydroxide (MOF-LDH) on the surface of the PU sponge. After grafting MOF-LDH with hexadecyltrimethoxysilane, FPUF@MOF-LDH@HDTMS showed excellent superhydrophobic/superoleophilic performance (water contact angle=153° and oil contact angle=0°). FPUF@MOF-LDH@HDTMS can easily and quickly adsorb oily liquids suspended/settled in the water thanks to the unique bionic structure. FPUF@MOF-LDH@HDTMS has excellent oil/organic solvents absorption capacity; even after 20 cycles of use still maintains high adsorption capacity. More importantly, the continuous oil-water separation through FPUF@MOF-LDH@HTMS has achieved a separation efficiency of up to 99.1%. In addition, the bionic superhydrophobic sponge has excellent flame retardancy, which reduces the possibility of secondary fire caused by PU sponges. Thus, the biomimetic micro-nano composite structure provides a new design strategy for the more high-performance oil-water separation sponges.
Assuntos
Incêndios , Retardadores de Chama , Estruturas Metalorgânicas , Poliuretanos , ÁguaRESUMO
Designing highly efficient, long-lasting, and cost-effective cathodic and anodic functional materials as a bifunctional electrocatalyst is essential for overcoming the bottleneck in fuel cell development. Herein, a novel two-step synthesis strategy is developed to synthesize metal-organic framework (MOF) derived nitrogen-doped carbon (NC) with improved spatial isolation and a higher loading amount of cobalt (Co) and nickel carbide (Ni3C) nanocrystal decorated on graphene (denoted as Co@NC-Ni3C/G). Benefiting from multiple active sites of high N-doping level, uniform dispersion of Co and Ni3C nanocrystals, and a large active area of graphene, the Co@NC-Ni3C/G hybrids exhibit excellent methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) efficiency in an alkaline environment. For MOR, the optimized Co@NC-Ni3C/G-350 catalyst achieved a current density of 44.8 mA cm-2 at an applied potential of 1.47 V (V vs. RHE), which is significantly higher than Co@NC-Ni3C (42.07 mA cm-2) and Co@NC (24.1 mA cm-2) in 0.5 M methanol + 1.0 M KOH solutions. In addition, during the CO retention test, the Co@NC-Ni3C/G-350 catalyst exhibits excellent CO tolerance capacity. Excitingly, the as-prepared Co@NC-Ni3C/G-350 hybrid exhibits significantly improved ORR catalytic efficiency in terms of positive onset and half-wave potential (Eonset = 0.90 V, E1/2 = 0.830 V vs. RHE), small Tafel slope (34 mV dec-1) and excellent durability (only reduced 0.016 V after 5000 s test). This work provides new insights into MOF-derived functional nanomaterials for anode and cathode co-catalysts for methanol fuel cells.
RESUMO
Two-dimensional (2D) layered metal carbides materials called MXenes (e.g., Ti3C2) are significantly attentioned as electrode material for lithium-ion capacitors (LICs) because of its large surface-to-volume ratio and ultra-high electronic conductivity. Whereas, as anode electrode material, the performance and application prospects of Ti3C2 are severely restricted to its lower theoretical capacity. In this work, a straightforward and effective strategy to surmount the restrictions was developed to combine layered Ti3C2 nanosheets with dual Co/Zn metal-organic framework (MOF) polyhedrons derivatives through electrostatic assembly. Co3O4/ZnO polyhedrons could prevent the stacking of Ti3C2 nanosheets and provide prominent lithium storage capacity. Furthermore, the advanced structure of Ti3C2@Co3O4/ZnO as anode material could provide short Li+ paths, large electrolyte channels and excellent structural stability to enhance the electrochemical performance for LICs. As a result, the prepared Ti3C2@Co3O4/ZnO composite exhibited a specific capacity of 585.7 mAh/g at 0.1 A/g, and the electrode still delivered a capacity of 229 mAh/g at 2 A/g after 1000 cycles with 93% capacity retention in lithium-ion half cell. In addition, by assembling with activated carbon (AC) as cathode and Ti3C2@Co3O4/ZnO as anode, the LIC revealed an ultra-high energy density of 196.8 Wh/kg at a power density of 174.9 W/kg, and delivered a high energy output of 87.5 Wh/kg even at a power density of 3500 W/kg. And its capacitance retention reaches 75% after 6000 cycles at 2 A/g. The advanced structure, handy preparation, and outstanding performance of layered carbon-based material Ti3C2@hollow polyhedrons composite might provide promising applications in LICs.
RESUMO
Practical implementation of periodate-based advanced oxidation processes for environmental remediation largely relies on the development of cost-effective and high-performance activators. Surface atomic engineering toward these activators is desirable but it remains challenging to realize improved activation properties. Here, a surface atomic engineering strategy used to obtain a novel hybrid activator, namely cobalt-coordinated nitrogen-doped graphitic carbon nanosheet-enwrapped cobalt nanoparticles (denoted as Co@NC-rGO), from a sandwich-architectured metal-organic framework/graphene oxide composite is reported. This activator exhibits prominent periodate activation properties toward pollutant degradation, surpassing previously reported transition-metal-based activators. Importantly, the activator shows good stability, magnetic reusability, and the potential for application in a complex water matrix. Density functional theory modeling implies that the strong activation capability of Co@NC-rGO is related to its surface atomic structure for which the embedded cobalt nanoparticles with abundant interfacial Co-N coordinations display modified electronic configurations on the active centers and benefit periodate adsorption. Quenching experiments and electrochemical measurements showed that the system could oxidize organics through a dominant nonradical pathway. Additionally, a lower concentration of cobalt leaching was observed for the Co@NC-rGO/periodate system than for its Co@NC-rGO/persulfate counterpart. Our work provides a pathway toward engineering surface atomic structures in hybrid activators for efficient periodate activation.
Assuntos
Poluentes Ambientais , Estruturas Metalorgânicas , Carbono , Descontaminação , Fenômenos Magnéticos , Ácido PeriódicoRESUMO
Metal-organic framework (MOF)-based materials with high porosity, tunable compositions, diverse structures, and versatile functionalities provide great scope for next-generation rechargeable battery applications. Herein, this review summarizes recent advances in pristine MOFs, MOF composites, MOF derivatives, and MOF composite derivatives for high-performance sodium-ion batteries, potassium-ion batteries, Zn-ion batteries, lithium-sulfur batteries, lithium-oxygen batteries, and Zn-air batteries in which the unique roles of MOFs as electrodes, separators, and even electrolyte are highlighted. Furthermore, through the discussion of MOF-based materials in each battery system, the key principles for controllable synthesis of diverse MOF-based materials and electrochemical performance improvement mechanisms are discussed in detail. Finally, the major challenges and perspectives of MOFs are also proposed for next-generation battery applications.
RESUMO
HIGHLIGHTS: Non-magnetic bimetallic MOF-derived porous carbon-wrapped TiO2/ZrTiO4 composites are firstly used for efficient electromagnetic wave absorption. The electromagnetic wave absorption mechanisms including enhanced interfacial polarization and essential conductivity are intensively discussed. Modern communication technologies put forward higher requirements for electromagnetic wave (EMW) absorption materials. Metal-organic framework (MOF) derivatives have been widely concerned with its diverse advantages. To break the mindset of magnetic-derivative design, and make up the shortage of monometallic non-magnetic derivatives, we first try non-magnetic bimetallic MOFs derivatives to achieve efficient EMW absorption. The porous carbon-wrapped TiO2/ZrTiO4 composites derived from PCN-415 (TiZr-MOFs) are qualified with a minimum reflection loss of - 67.8 dB (2.16 mm, 13.0 GHz), and a maximum effective absorption bandwidth of 5.9 GHz (2.70 mm). Through in-depth discussions, the synergy of enhanced interfacial polarization and other attenuation mechanisms in the composites is revealed. Therefore, this work confirms the huge potentials of non-magnetic bimetallic MOFs derivatives in EMW absorption applications.
RESUMO
To tackle the aggravating electromagnetic wave (EMW) pollution issues, high-efficiency EMW absorption materials are urgently explored. Metal-organic framework (MOF) derivatives have been intensively investigated for EMW absorption due to the distinctive components and structures, which is expected to satisfy diverse application requirements. The extensive developments on MOF derivatives demonstrate its significantly important role in this research area. Particularly, MOF derivatives deliver huge performance superiorities in light weight, broad bandwidth, and robust loss capacity, which are attributed to the outstanding impedance matching, multiple attenuation mechanisms, and destructive interference effect. Herein, we summarized the relevant theories and evaluation methods, and categorized the state-of-the-art research progresses on MOF derivatives in EMW absorption field. In spite of lots of challenges to face, MOF derivatives have illuminated infinite potentials for further development as EMW absorption materials.