Single-crystal X-ray diffraction is a powerful characterization technique that enables the determination of atomic arrangements in crystalline materials. Growing or retaining large single crystals amenable to it has, however, remained challenging with covalent organic frameworks (COFs), especially suffering from post-synthetic modifications. Here we show the synthesis of a flexible COF with interpenetrated qtz topology by polymerization of tetra(phenyl)bimesityl-based tetraaldehyde and tetraamine building blocks. The material is shown to be flexible through its large, anisotropic positive thermal expansion along the c axis (αc = +491 × 10-6 K-1), as well as through a structural transformation on the removal of solvent molecules from its pores. The as-synthesized and desolvated materials undergo single-crystal-to-single-crystal transformation by reduction and oxidation of its imine linkages to amine and amide ones, respectively. These redox-induced linkage conversions endow the resulting COFs with improved stability towards strong acid; loading of phosphoric acid leads to anhydrous proton conductivity up to ca. 6.0 × 10-2 S cm-1.
Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two-dimensional (2D) material, Cu-(4-mercaptophenol) (Cu-HBT), as a passivator precursor. Cu-HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu-HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin-coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu-HBT and convert in situ into p-type semiconductors, Cu2 S and PbS. The resultant Cu2 S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs.
Herein, we present a new series of CuI-based hybrid materials with tunable structures and semiconducting properties. The CuI inorganic modules can be tailored into a one-dimensional (1D) chain and two-dimensional (2D) layer and confined/stabilized in coordination frameworks of potassium isonicotinic acid (HINA) and its derivatives (HINA-R, R = OH, NO2, and COOH). The resulting CuI-based hybrid materials exhibit interesting semiconducting behaviors associated with the dimensionality of the inorganic module; for instance, the structures containing the 2D-CuI module demonstrate significantly enhanced photoconductivity with a maximum increase of five orders of magnitude compared to that of the structures containing the 1D-CuI module. They also represent the first CuI-bearing hybrid chemiresistive gas sensors for NO2 with boosted sensing performance and sensitivity at multiple orders of magnitude over that of the pristine CuI. Particularly, the sensing ability of CuI-K-INA containing both 1D- and 2D-CuI modules is comparable to those of the best NO2 chemiresistors reported thus far.
The electronic conductivity (EC) of metal-organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H2 O on the EC of MOFs is rarely reported. We explored the effect of H2 O on the EC in the MOFs (NH2 )2 -MIL-125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 107 on H2 SO4 @(NH2 )2 -MIL-125 by H2 O was observed. Brønsted acid-base pairs formed with the -NH2 groups, and H2 SO4 played an important role in promoting the charge transfer from H2 O to the MOF. Based on H2 SO4 @(NH2 )2 -MIL-125, a high-performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H2 O can remarkably influence the EC of MOFs, but it also revealed that post-modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high-performance sensing materials.
Surface modification is a promising method to change the surface properties of nanomaterials, but it is limited in enhancing their intrinsic redox nature. In this work, a "filter amplifier" strategy is proposed for the first time to reverse the intrinsic redox nature of materials. This is demonstrated by coating a COF-316 layer with controlled thickness on TiO2 to form core-sheath nanowire arrays. This unique structure forms a Z-scheme heterojunction to function as "a filter amplifier" which can conceal the intrinsic oxidative sites and increase the extrinsic reductive sites. Consequently, the selective response of TiO2 is dramatically reversed from reductive ethanol and methanol to oxidative NO2. Moreover, TiO2@COF-316 provides remarkably improved sensitivity, response, and recovery speed, as well as unusual anti-humidity properties as compared with TiO2. This work not only provides a new strategy to rationally modulate the surface chemistry properties of nanomaterials but also opens an avenue to design high-performance electronic devices with a Z-scheme heterojunction.
Hydrogen-bonded organic frameworks (HOFs) are a rising class of promising proton-conducting materials. However, they always suffer from the inherent contradiction between chemical stability and proton conduction. Herein, inspired by the self-assembly of lipid bilayer membranes, a series of aminomethylphosphonic acid-derived single-component HOFs are successfully developed with different substituents attached to the phosphonate oxygen group. They remain highly stable in strong acid or alkaline water solutions for one month owing to the presence of charge-assisted hydrogen bonds. Interestingly, in the absence of external proton carriers, the methyl-substituted phosphonate-based HOF exhibits a very high proton conductivity of up to 4.2 × 10-3 S cm-1 under 80 °C and 98% relative humidity. This value is not only comparable to that of HOFs consisting of mixed ligands but also is the highest reported in single-component HOFs. A combination of single-crystal structure analysis and density functional theory calculations reveals that the high conductivity is attributed to the strengthened H-bonding interactions between positively charged amines and negatively charged phosphonate groups in the channel of bio-inspired HOFs. This finding demonstrates that the well-defined molecular structure of proton conductors is of great importance in the precise understanding of the relationship between structure and property.
The layer-by-layer liquid-phase epitaxy (LBL-LPE) method is widely used in preparing metal-organic framework (MOF) thin films with the merits of controlling thickness and out-of-plane orientation for superior performances in applications. The LBL-LPE growth mechanism related to the grain boundary, structure defect, and orientation is critical but very challenging to study. In this work, a novel "in-plane self-limiting and self-repairing" thin-film growth mechanism is demonstrated by the combination study of the grain boundary, structure defect, and orientation of Cu3 (HHTP)2 -xC thin film via microscopic analysis techniques and electrical measurements. This mechanism results a desired high-quality MOF thin film with preferred in-plane orientations at its bottom for the first time and is very helpful for optimizing the LBL-LPE method, understanding the growth cycle-dependent properties of MOF thin film, and inspiring the investigations of the biomimetic self-repairing materials.
Accurate fire warning is very important for people's life and property safety. The most commonly used fire alarm is based on the detection of a single factor of gases, smoke particles, or temperature, which easily causes false alarm due to complex environmental conditions. A facile multi-factor route for fabricating an accurate analog fire alarm using a Pb5 S2 I6 nanowire mesh based on its photoelectric and gas-sensing dual function is presented. The Pb5 S2 I6 nanowire mesh presents excellent photoelectric detection capabilities and is sensitive to ppm-level NO2 at room temperature. Under the "two-step verification" circuit of light and gas factors, the bimodal simulation fire alarm based on this Pb5 S2 I6 nanowire mesh can resist the interference of complex environmental factors and effectively reduce the false alarm rate.
Fires , Nanowires , Gases , Humans , Lead , Surgical Mesh
Challenges remain in the development of novel multifunctional electrocatalysts and their industrial operation on low-electricity pair-electrocatalysis platforms for the carbon cycle. Herein, an enzyme-inspired single-molecular heterojunction electrocatalyst ((NHx )16 -NiPc/CNTs) with specific atomic nickel centers and amino-rich local microenvironments for industrial-level electrochemical CO2 reduction reaction (eCO2 RR) and further energy-saving integrated CO2 electrolysis is designed and developed. (NHx )16 -NiPc/CNTs exhibit unprecedented catalytic performance with industry-compatible current densities, ≈100% Faradaic efficiency and remarkable stability for CO2 -to-CO conversion, outperforming most reported catalysts. In addition to the enhanced CO2 capture by chemisorption, the sturdy deuterium kinetic isotope effect and proton inventory studies sufficiently reveal that such distinctive local microenvironments provide an effective proton ferry effect for improving local alkalinity and proton transfer and creating local interactions to stabilize the intermediate, ultimately enabling the high-efficiency operation of eCO2 RR. Further, by using (NHx )16 -NiPc/CNTs as a bifunctional electrocatalyst in a flow cell, a low-electricity overall CO2 electrolysis system coupling cathodic eCO2 RR with anodic oxidation reaction is developed to achieve concurrent feed gas production and sulfur recovery, simultaneously decreasing the energy input. This work paves the new way in exploring molecular electrocatalysts and electrolysis systems with techno-economic feasibility.
The modification of inorganic two-dimensional (2D) materials with organic functional motifs is in high demand for the optimization of their properties, but it is still a daunting challenge. Organic metal chalcogenides (OMCs) are a type of newly emerging 2D materials, with metal chalcogenide layers covalently anchored by long-range ordered organic functional motifs, these materials are extremely desirable but impossible to realize by traditional methods. Both the inorganic layer and organic functional motifs of OMCs are highly designable and thus provide this type of 2D materials with enormous variety in terms of their structure and properties. This Minireview aims to review the latest developments in OMCs and their bulk precursors. Firstly, the structure types of the bulk precursors for OMCs are introduced. Second, the synthesis and applications of OMC 2D materials in photoelectricity, catalysis, sensors, and energy transfer are explored. Finally, the challenges and perspectives for future research on OMCs are discussed.
A new 2D fluorescent organic-metal chalcogenide (OMC), CdClHT (HT = 4-hydroxythiophenol), evenly covered with phenol groups is reported. CdClHT represents unparalleled selectivity and the highest sensitivity towards 2,4,6-trinitrophenol (TNP) (KSV = 2.16 × 107 m-1, experimental LOD = 2 nM), among all reported 2D conjugated polymer (CP) luminescent detectors.
Luminescent metal-organic frameworks (LMOFs) with diverse structural features and promising fluorescence-based applications have attracted wide attention in the past two decades. In this work, a LMOF with the formula [Ca4(tcbpe-F)2(H2O)3] (1, LMOF-411) has been constructed from calcium (Ca) and 1,1,2,2-tetrakis(4-(4-carboxyphenyl)phenyl)ethene (H4tcbpe-F). Compound 1 features a three-dimensional framework with a 10-nodal net topology. Due to the relatively high hydration energy of Ca2+, compound 1 readily transforms into a new phase formulated as [Ca(H2tcbpe-F)(H2O)2] (1') upon exposure to water. Combining experimental characterization and theoretical calculations, we elucidated the mechanism of H2O-induced phase transition from 1 to 1'. Notably, the water induced phase transformation can be detected visibly from the change in luminescence, which originates from the fluorescent linker. Compound 1 emits green light (λ em = 490 nm) under UV excitation, while compound 1' emits bright yellow light (λ em = 550 nm) under blue excitation (450 nm). Compound 1' represents the first Ca based LMOF yellow phosphor and its luminescence quantum yield reaches 68%. It can be coated directly onto a commercial blue light-emitting-diode (LED) chip to fabricate a white LED (WLED).
Metal-organic frameworks (MOFs) built from different building units offer functionalities going far beyond gas storage and separation. In connection with advanced applications, e.g., in optoelectronics, hierarchical MOF-on-MOF structures fabricated using sophisticated methodologies have recently become particularly attractive. Here, we demonstrate that the structural complexity of MOF-based architectures can be further increased by employing highly spatioselective photochemistry. Using a layer-by-layer, quasi-epitaxial synthesis method, we realized a photoactive MOF-on-MOF hetero-bilayer consisting of a porphyrinic bottom layer and a tetraphenylethylene (TPE)-based top layer. Illumination of the monolithic thin film with visible light in the presence of oxygen gas results in the generation of reactive oxygen species (1O2) in the porphyrinic bottom layer, which lead to a photocleavage of the TPE units at the internal interface. We demonstrate that this spatioselective photochemistry can be utilized to delaminate the top layers, yielding two-dimensional (2D) MOF sheets with well-defined thickness. Experiments using atomic force microscopy (AFM) demonstrate that these platelets can be transferred onto other substrates, thus opening up the possibility of fabricating planar MOF structures using photolithography.
The construction of hydrophobic nanochannel with hydrophilic sites for bionic devices to proximally mimick real bio-system is still challenging. Taking the advantages of MOF chemistry, a highly oriented CuTCPP thin film has been successfully reconstructed with ultra-thin nanosheets to produce abundant two-dimensional interstitial hydrophobic nanochannels with hydrophilic sites. Different from the classical active-layer material with proton transport in bulk, CuTCPP thin film represents a new type of active-layer with proton transport in nanochannel for bionic proton field-effect transistor (H+ -FETs). The resultant device can reversibly modulate the proton transport by varying the voltage on its gate electrode. Meanwhile, it shows the highest proton mobility of ≈9.5×10-3 â cm2 V-1 s-1 and highest on-off ratio of 4.1 among all of the reported H+ -FETs. Our result demonstrates a powerful material design strategy for proximally mimicking the structure and properties of bio-systems and constructing bionic electrical devices.
Artificial transistors represent an ideal means for meeting the requirements in interfacing with biological systems. It is pivotal to develop new proton-conductive materials for the transduction between biochemical events and electronic signals. Herein, the first demonstration of a porous organic polymer membrane (POPM) as a proton-conductive material for protonic field-effect transistors is presented. The POPM is readily prepared through a thiourea-formation condensation reaction. Under hydrated conditions and at room temperature, the POPM delivers a proton mobility of 5.7 × 10-3 cm2 V-1 s-1 ; the charge carrier densities are successfully modulated from 4.3 × 1017 to 14.1 × 1017 cm-3 by the gate voltage. This study provides a type of promising modular proton-conductive materials for bioelectronics application.
Engineering the band gap chemically by organic molecules is a powerful tool with which to optimize the properties of inorganic 2D materials. The obtained materials are however still limited by inhomogeneous compositions and properties at nanoscale and small adjustable band gap ranges. To overcome these problems in the traditional exfoliation and then organic modification strategy, an organic modification and then exfoliation strategy was explored in this work for preparing 2D organic metal chalcogenides (OMCs). Unlike the reported organically modified 2D materials, the inorganic layers of OMCs are fully covered by long-range ordered organic functional groups. By changing the electron-donating ability of the organic functional groups and the electronegativity of the metals, the band gaps of OMCs were varied by 0.83 eV and their conductivities were modulated by 9 orders of magnitude, which are 2 and 107 times higher than the highest values observed in the reported chemical methods, respectively.
Introducing porous material into optical cavities is a critical step toward the utilization of quantum-electrodynamical (QED) effects for advanced technologies, e.g. in the context of sensing. We demonstrate that crystalline, porous metal-organic frameworks (MOFs) are well suited for the fabrication of optical cavities. In going beyond functionalities offered by other materials, they allow for the reversible loading and release of guest species into and out of optical resonators. For an all-metal mirror-based Fabry-Perot cavity we yield strong coupling (â¼21% Rabi splitting). This value is remarkably large, considering that the high porosity of the framework reduces the density of optically active moieties relative to the corresponding bulk structure by â¼60%. Such a strong response of a porous chromophoric scaffold could only be realized by employing silicon-phthalocyanine (SiPc) dyes designed to undergo strong J-aggregation when assembled into a MOF. Integration of the SiPc MOF as active component into the optical microcavity was realized by employing a layer-by-layer method. The new functionality opens up the possibility to reversibly and continuously tune QED devices and to use them as optical sensors.
[This corrects the article DOI: 10.1039/D0SC02436H.].
Herein, we report two nanocluster-based compounds built on an unprecedented cluster [Ba13Sb36Cl34O54]8-, which represents the first example of a discrete alkaline earth (AE)-containing oxochloride cluster and the largest Sb-based oxohalide cluster to date; the proton-conducting property of the compounds was investigated.
Photoconductivity is a characteristic property of semi-conductors. Herein, we present a photo-conducting crystalline metal-organic framework (MOF) thin film with an on-off photocurrent ratio of two orders of magnitude. These oriented, surface-mounted MOF thin films (SURMOFs), contain porphyrin in the framework backbone and C60 guests, loaded in the pores using a layer-by-layer process. By comparison with results obtained for reference MOF structures and based on DFT calculations, we conclude that donor-acceptor interactions between the porphyrin of the host MOF and the C60 guests give rise to a rapid charge separation. Subsequently, holes and electrons are transported through separate channels formed by porphyrin and by C60 , respectively. The ability to tune the properties and energy levels of the porphyrin and fullerene, along with the controlled organization of donor-acceptor pairs in this regular framework offers potential to increase the photoconduction on-off ratio.
