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MOFs can provide atomically dispersed metal active coordination sites (M-NX, M-SX, M-OX) for electrocatalytic reactions. Among them, MOFs with motif M-NX or analogues are expected to be promising a...

Based on the theories of geography and landscape ecology, land ecological restoration is an important strategy to promote ecological civilization and build a beautiful China. Land ecological restoration in China has the characteristics of multi-disciplinary theoretical system, diverse work mode, integration of technology and methods, and diversified practice and exploration. The overall effectiveness of the work coexists with arduous tasks. Based on the new challenges in land ecological restoration, we summarized the overall framework and technical path of land ecological restoration, the working mechanism and mode of regional land ecological restoration, the content system and technical standards of land ecological restoration. In the new stage, the top-level design of land ecological restoration in China should focus on the work system, business boundary and institutional system, identify the responsibility boundary of different business processes, and realize the closed management of the whole work chain from the perspective of theory, system, engineering and technology. Rural settlement area, urban built-up area, industrial and mining gathering area, ecological function area and blue ocean area are the five major elements of regional scale land space, which correspond to five different ecological restoration modes, namely, comprehensive land improvement, urban renewal and double repair, mine geological environment restoration, mountain-river-forest-farmland-lake-grassland restoration, and blue bay restoration. It is necessary to comprehensively use the thinking of "Three Integrations" (information, technology, and process) to build a set of regional land ecological restoration work mode covering the integration of investigation, monitoring and evaluation, land space planning, project implementation, project acceptance and ecosystem monitoring and evaluation.国土空间生态修复以地理学、景观生态学理论为基础,是推进生态文明、建设美丽中国的重要举措。我国国土空间生态修复呈现理论体系多学科化、工作模式多元化、技术方法融合化、实践探索多样化的特征,工作总体成效显著与任务艰巨并存。本文基于国土空间生态修复的新挑战,对国土空间生态修复研究的总体框架和技术路径、区域国土空间生态修复的工作机制与模式、国土空间生态修复的内容体系和技术标准进行综述。新时期,我国国土空间生态修复顶层设计应重点围绕工作体系、业务边界和制度体系3项内容,明确各类业务流程的职责边界,从理论、制度、工程、技术全域视角实现工作全链条闭合管理。乡村聚落区、城镇建成区、工矿聚集区、生态功能区、蓝色海洋区是区域尺度国土空间的5大组成要素,分别对应全域土地综合整治、城市更新与城市双修、矿山地质环境修复治理、山水林田湖草系统修复、蓝色海湾修复整治5种差别化生态修复模式。应综合运用“三个集成”(信息、技术、流程)思维,构建一套涵盖调查监测评价、国土空间规划、工程项目实施、工程项目验收、生态系统监测评价一体化的区域国土空间生态修复工作模式。.

The oxygen reduction reaction (ORR) is a crucial step in fuel cells and metal-air batteries. It is necessary to expand the range of efficient non-precious ORR electrocatalysts on account of the low abundance and high cost of Pt/C catalysts. Herein, we synthesized crystalline cobalt-embedded N-doped carbon nanotubes (Co@CNTs-T) via facile carbonization of Co/Zn metal-organic frameworks (MOFs) with dicyandiamide at different temperatures (t = 600, 700, 800, 900 &deg, C). Co@CNTs- 800 possessed excellent ORR activities in alkaline electrolytes with a half wave potential of 0.846 V vs. RHE (Reversible Hydrogen Electrode), which was comparable to Pt/C. This three-dimensional network, formed by Co@CNTs-T, facilitated electron migration and ion diffusion during the ORR process. The carbon shell surrounding the Co nanoparticles resulted in Co@CNTs-800 being stable as an electrocatalyst. This work provides a new strategy to design efficient and low-cost oxygen catalysts.

Metal-organic frameworks (MOFs) can provide atomically dispersed metal active coordination sites (M-N

Carbon-coated NiO/reduced graphene oxide (NiO/rGO) composites with NiO nanoparticles (∼5 nm) homogeneously distributed and carbon skeletons on the surface were constructed in this work. Graphene ox...

A sensitive and specific photoelectrochemical (PEC) immunosensor was fabricated for subgroup J avian leukosis viruses (ALV-J) analysis based on a dual signal-on strategy. Gold nanoparticles (AuNPs) decorated graphitic carbon nitride (AuNPs/g-C3N4) as photoelectrochemical species and primary antibody (Ab1) against ALV-J were immobilized onto ITO electrode in turn. An ALP-CdTe-Ab2 bio-conjugant was fabricated by assembling second antibody (Ab2) and alkaline phosphatase (ALP) to CdTe quantum dots (QDs) surface. The PEC immunosensor was fabricated by successively anchoring the target ALV-J and ALP-CdTe-Ab2 bio-conjugants onto electrode surface via the immune recognition. By virtue of the matched energy levels between CdTe QDs and AuNPs/g-C3N4, ALP-CdTe-Ab2 bio-conjugants could serve as the PEC active probes for photocurrent enhancement. Moreover, the photocurrent response could be further enhanced attributed to the ALP catalytic chemistry to in situ produce ascorbic acid for electron donating, achieving an effective dual signal-on mode for PEC assay. On the basis of the ALV-J titers-dependent photocurrent increment, the fabricated PEC immunosensor showed high sensitivity, specificity and stability for ALV-J assay in a wide linear range with a low detection limit of 85 TCID50/mL. This PEC immunosensor with the dual signal-on strategy may open up a promising platform for more target analytes in novel immune analysis and clinical diagnostics.

The facile synthesis of polyaniline/Bi2MoO6 (PANIx/Bi2MoO6) nanocomposites for visible-light-driven degradation of rhodamine B (RhB) was developed via in situ polymerization of PANI on the surface of Bi2MoO6 nanosheets as robust photocatalysts. The molecular PANI layers covered the surface of flower-like Bi2MoO6 microspheres consisting of ultrathin nanosheets (13.8 ± 1.6 nm) and exerted no impact on the intrinsic crystallinity of Bi2MoO6. The PANI/Bi2MoO6 exhibited enhanced visible light absorbance, improved photoelectrochemical performance and remarkably increased photocatalytic efficiency in the degradation of RhB. The synergistic effect of the well-matched band structures of Bi2MoO6 and PANI coupled with the molecular PANI layers for excellent hole transfer and accessible active sites contributed to the enhanced separation efficiency of photogenerated charge carriers and the boosted photocatalytic activity for RhB removal. Mechanism studies indicated that the photoinduced holes and superoxide radicals played essential roles in the enhanced photocatalytic performance. The optimized photodegradation rate for RhB was up to ∼100% during 120 min in the case of PANI0.5/Bi2MoO6, which revealed the first-order kinetics with a high apparent rate constant of 0.0335 min−1 and acceptable recycling stability. This work sheds light on the application of Bi2MoO6-based photocatalysts with superior photocatalytic activity in environmental remediation.

Manipulating the morphology of chalcogenide semiconductor crystals to tailor their shape- and size-dependent properties is much desired but remains a grand challenge. Herein, we for the first time develop a green, facile and surfactant-free hydrothermal approach for the synthesis of bismuth sulfide (Bi2S3) with highly tunable morphologies in H2WO4 aqueous solution. The H2WO4 is prone to balance the concentration of Bi3+ to S2− in aqueous solution, thus modulating the nucleation and epitaxial growth of Bi2S3. Specifically, in the presence of lower H2WO4 concentration, the low number of Bi2S3 nuclei facilitates the preferred growth of nanorod structures along the [001] direction, while the Bi-deficient, S-rich conditions in higher H2WO4 concentration give rise to Bi2S3 nanotubes, presumably due to the stronger interlayer interaction and preferred growth in the [hk0] direction. The resulting Bi2S3 nanostructures exhibit broad absorption overlapping UV-visible-NIR regions and red-shifted absorption edges owing to the increased S/Bi molar ratio in Bi2S3 lattices. The Bi2S3 nanorods with a higher aspect ratio demonstrate an enhanced photocurrent response by virtue of the improved charge carrier mobility along the [001] direction. Different from previous synthetic methodologies, this work details a facile, effective, and environmentally-benign protocol for the synthesis of Bi2S3 nanomaterials in the aqueous medium without any organic reagents. Notably, the excellent and tailorable photoelectrochemical (PEC) performance endows these Bi2S3 nanostructures with vast potential in solar cell and photodetector applications.

The morphologies and structures of nanostructured carbons generally influence their catalysis, electrochemical performance and adsorption properties. Metal-organic framework (MOF) nanocrystals usually have various morphologies, and can be considered as a template to construct nanostructured carbons with shaped nanocubes, nanorods, and hollow particles by thermal transformation. However, thermal carbonization of MOFs usually leads to collapse of MOF structures. Here, we report shape-preserved carbons (termed as CNRods) by thermal transformation of nickel catecholate framework (Ni-CAT) nanorods. Supercapacitors of CNRods treated at 800 °C were demonstrated to have enhanced performance due to their structural features that facilitate electron conduction and ion transport as well as abundant O content benefiting the wettability of the carbon materials. This may provide a potential way to explore novel carbon materials for supercapacitors with controllable morphologies and high capacitive performance.

Here, we report the design of upconversion nanoparticle-coupled perovskite quantum dots that are full-color tunable under single near-infrared (NIR) excitation. Consequently, we demonstrate the use of these hybrid nanomaterials in printable, NIR-excitable, dual-model anti-counterfeiting.

Polymorphic single-layered covalent organic frameworks (sCOFs) via on-surface synthesis have been investigated by employing the tetradentate monomer 1,3,6,8-tetrakis(p-formylphenyl)pyrene with D2h symmetry and ditopic linear diamine building blocks. Three kinds of well-ordered sCOFs, including rhombus, parallelogram, and Kagome networks, are observed on the graphite surface by scanning tunnel microscopy. The pore size and periodicity of sCOFs are tunable by employing diamine monomers with different lengths. Statistical analysis reveals that two types of quadrate networks are preferred at high concentration, whereas the occupancy of Kagome networks increases at low concentration. This trend can be understood by the differences in the network density of three kinds of networks. The reversibility and the self-sorting ability of the dynamic covalent reaction make it possible to control the polymorphic distribution similar to the principle demonstrated in supramolecular self-assembly.

Metal–nitrogen coordination sites, M–Nx (M = Fe, Co, Ni, etc.), have shown great potential to replace platinum group materials as electrocatalysts for oxygen reduction reaction (ORR). However, the real active site in M–Nx is still vague to date due to their complicated structure and composition. It is therefore highly desirable but challenging to develop ORR catalysts with novel and clear active sites, which could meet the needs of comprehensive understanding of structure–function relationships and explore new cost-effective and efficient ORR electrocatalysts. Herein, well-defined M–O6 coordination in metal–catecholates (M–CATs, M = Ni or Co) is discovered to be catalytically active for ORR via a four-electron-dominated pathway. In view of no pyrolysis involved and unambiguous crystalline structure of M–CATs, the M–O6 octahedral coordination site with distinct structure is determined as a new type of active site for ORR. These findings extend the scope of metal–nonmetal coordination as an active site for ...

The inherent periodically arranged M−NX, M−SX and M−OX units (M are usually Fe, Co, Ni, etc.) in metal–organic frameworks (MOFs) can be promising active centers in electrocatalysis. In previous studies, MOFs were usually constructed by energy-consuming hydro- or solvo-thermal reactions. Ultrasonic synthesis is a rapid and environment-friendly technique when envisaging MOFs’ industrial applications. In addition, different synthetic pathways for MOFs may lead to difference in their microstructure, resulting in different electrocatalytic performance. Nevertheless, only a handful of MOFs were successfully prepared by ultrasonic synthesis and few were applied in electrochemical catalysis. Herein, we constructed Ni/Co-catecholates (Ni/Co-CATs) synthesized by one-step ultrasonic method (250 W, 40 KHz, 25 W/L, Ultrasonic clearing machine) and compared their performance in oxygen reduction reaction (ORR) with that of Ni/Co-CATs synthesized by hydrothermal method. Ni-CAT and Co-CAT prepared by ultrasonic showed the half-wave potential of −0.196 V and −0.116 V (vs. Ag/AgCl), respectively. The potentials were more positive than those prepared by hydro-thermal method. And they showed excellent electrochemical stability in neutral solution. The latter was only 32 mV lower than that of commercial Pt/C. The improved performance in ORR was attributed to higher specific surface area and mesopore volume as well as more structural defects generated in the ultrasonic synthesis process, which could facilitate their exposure of electrocatalytic active sites and their mass transport. This work gives some perspective into cost-effective synthetic strategies of efficient MOFs-based electrocatalysts.

Redox-active polyimide materials hold a great promise for electrochemical energy storage applications, especially for flexible energy storage devices. However, the low utilization efficiency due to poor electrical conductivity of the materials remains one of the greatest challenges. In this work, we designed and prepared polyimide-graphene composite materials and tested their electrochemical properties in sodium-ion capacitors. By manipulating the interfacial chemistry and interactions between the polyimide and graphene, composite electrode materials with different polyimide particle sizes and morphologies were obtained. Sodium-ion storage capacity was significantly improved, from ∼50 mAh g-1 for pure polyimide to 225 mAh g-1 for a polyimide-graphene composite. A hybrid sodium-ion capacitor fabricated with freestanding polyimide-graphene composite as the negative electrode and reduced graphene oxide as the positive electrode delivered energy densities of 55.5 and 21.5 Wh kg-1 at power densities of 395 and 3400 W kg-1, respectively. A flexible sodium-ion capacitor with outstanding mechanical properties was also demonstrated.

The design and construction of stable porous networks featuring tunable cavities for selective guest inclusion remains a great challenge in construction of functional miniature devices. Herein we report on construction and guest inclusion of stable 2D porphyrin-based molecular square grids connected by imine bonds showing crystalline pattern with periodic square cavities. Diperylene diimides molecules can be decorated into the square pores of the porphyrin-based molecular template on HOPG surfaces. The periodicity control over the covalent molecular grid and thus that of guest molecules is demonstrated by changing the building block. The preparation of robust host–guest systems may facilitate the fabrication of molecular miniature devices with designable properties.

MnWO4 nano photocatalysts with plate shapes and in high yields are in situ synthesized on the surface of a porous TiO2 film by the conventional plasma electrolytic oxidation (PEO) method combined with a subsequent ambient annealing process. Transmission electron microscopy (TEM) analysis shows that the MnWO4 nano photocatalysts are single crystals free of structural defects and scanning electron microscopy (SEM) observation on the cross-section reveals that these MnWO4 nano photocatalysts are in situ grown on the porous TiO2 film surface with strong adhesion. The morphology and dimension size can be selectively tailored through controlling the reaction time, showing the simplicity and versatility of the proposed method. In addition, the photodegradation of methylene blue (MB) solution using the MnWO4/TiO2 photocatalysts demonstrated the superior photocatalytic performance with high efficiency and excellent photostability. A high photodegradation rate of MB solution of over 90% in 60 min has been achieved and a superior cyclic capability is also obtained. The superior photocatalytic performance of MnWO4/TiO2 photocatalysts can be mainly attributed to the good crystallinity, all-surface covering and strong mechanical properties of the MnWO4 nanostructures with TiO2 film. The prevailing advantage of the PEO method in combination with the ambient annealing process will open up more opportunity for the rational synthesis of a wide range of oxide photocatalysts ranging from tungstate to titanate, molybdate and vanadate for promising catalytic applications in diverse fields.

Metal-nitrogen coordination sites, M-N

The construction of a spatially defined assembly of molecular building blocks, especially in the vertical direction, presents a great challenge for surface molecular engineering. Herein, we demonstrate that an electric field applied between an STM tip and a substrate triggered the formation of a bilayer structure at the solid-liquid interface. In contrast to the typical high electric-field strength (10(9) V m(-1) ) used to induce structural transitions in supramolecular assemblies, a mild electric field (10(5) V m(-1) ) triggered the formation of a bilayer structure of a polar molecule on top of a nanoporous network of trimesic acid on graphite. The bilayer structure was transformed into a monolayer kagome structure by changing the polarity of the electric field. This tailored formation and large-scale phase transformation of a molecular assembly in the perpendicular dimension by a mild electric field opens perspectives for the manipulation of surface molecular nanoarchitectures.

Using a fully nonlinear two-dimensional (2-D) numerical model, we simulated gravity waves (GWs) breaking and their contributions to the formation of large winds and wind shears in the mesosphere and lower thermosphere (MLT). An eddy diffusion coefficient is used in the 2-D numerical model to parameterize realistic turbulent mixing. Our study shows that the momentum deposited by breaking GWs accelerates the mean wind. The resultant large background wind increases the GW's apparent horizontal phase velocity and decreases the GW's intrinsic frequency and vertical wavelength. Both the accelerated mean wind and the decreased GW vertical wavelength contribute to the enhancement of wind shears. This, in turn, creates a background condition that favors the occurrence of GW instability, breaking, and momentum deposition, as well as mean wind acceleration, which further enhances the wind shears. We find that GWs with longer vertical wavelengths and faster horizontal phase velocity can induce larger winds, but they may not necessarily induce larger wind shears. In addition, the background temperature can affect the time and height of GW breaking, thus causing accelerated mean winds and wind shears.

Surface covalent organic frameworks (SCOFs), featured by atomic thick sheet with covalently bonded organic building units, are promised to possess unique properties associated with reduced dimensionality, well-defined in-plane structure, and tunable functionality. Although a great deal of effort has been made to obtain SCOFs with different linkages and building blocks via both "top-down" exfoliation and "bottom-up" surface synthesis approaches, the obtained SCOFs generally suffer a low crystallinity, which impedes the understanding of intrinsic properties of the materials. Herein, we demonstrate a self-limiting solid-vapor interface reaction strategy to fabricate highly ordered SCOFs. The coupling reaction is tailored to take place at the solid-vapor interface by introducing one precursor via vaporization to the surface preloaded with the other precursor. Following this strategy, highly ordered honeycomb SCOFs with imine linkage are obtained. The controlled formation of SCOFs in our study shows the possibility of a rational design and synthesis of SCOFs with desired functionality.

The introduction of intramolecular H-bonding by adding –OH functionalities adjacent to the Schiff base centers is considered to be a useful strategy to enhance the stability and crystallinity of bulk covalent organic frameworks (COFs). However, the influence of intramolecular H-bonding on the synthesis of surface COFs (SCOFs) have been barely explored. Herein, SCOFs based on the Schiff-base reaction between 1,3,5-tris(4-aminophenyl)benzene (TAPB) and terephthalaldehydes with symmetry or asymmetrically substituted hydroxyl functional groups are designed. In the absence of a solvent, hydroxyl substituents can be easily oxidized; thus argon protection is required to obtain high-quality SCOFs. Besides, an extended network with uniform pores can be achieved in spite of the symmetry of substituents. Both experimental results and theoretical calculations show that the influence of intramolecular hydrogen bonding on surface synthesis is not as important as that in bulk phase synthesis because the substrate itself can lead to the complanation of adsorbed molecules. The existence of intramolecular H-bonding can enhance the stability of the network in both acid and alkali environments.

A pair of isomeric imine-based covalent organic frameworks with non-aromatic linkage has been fabricated at the graphite surface, which extends the structural diversity of surface covalent organic frameworks.

Halogen bonding has attracted much attention recently as an important driving force for supramolecular assembly and crystal engineering. Herein, we demonstrate for the first time the formation of a halogen bond-based open porous network on a graphite surface using ethynylpyridine and aryl-halide based building blocks. We found that the electrical stimuli of a scanning tunneling microscopy (STM) tip can induce the formation of a binary supramolecular structure on the basis of halogen bond formation between terminal pyridyl groups and perfluoro-iodobenzene. This electrical manipulation method can be applied to engineer a series of linear or porous structures by selecting halogen bond donor and acceptor fragments with different symmetries, as the directional interactions ultimately determine the structural outcome.

Electrical transport properties of a Schottky junction consisting of carbon nanotube and nitrogen-doped carbon nanotube were studied. The current-voltage characteristics of the junction exhibited reproducible rectifying behavior which could be explained by the Schottky barrier junction. The barrier height and the ideal factor were determined by fitting the current-voltage characteristics to the generalized diode equation. A near power-law dependence of I∼Vm was observed, where the exponent m increases with decreasing temperature. This effect can be accounted for by filling of deep traps at lower temperatures. The charge transport in the nanotubes is found to be strongly controlled and limited by the highly defective trap state originated from structural and chemical defects due to the doping of nitrogen in the CNx nanotube part.

The quaternary InAlGaN films were grown by metal-organic vapor phase epitaxy (MOVPE) at various temperatures and the optical and structural properties of the quaternary films were investigated by temperature-dependent photoluminescence (PL), high-resolution X-ray diffraction (HRXRD) and high-resolution electron microscopy (HREM). The results show that the temperature-dependent PL intensity of the InAlGaN film is similar to that of the disordered alloys, which is thought to be due to local alloy compositional fluctuations (ACF) in the epilayer. HRXRD measurement reveals there are In-rich and In-poor phases in the film and HREM observation, on the other hand, demonstrates that nanoclusters formed in the epilayer. Therefore the experimental results support the existence of ACF in the epilayers.

With graphene-like topology and designable functional moieties, single-layered covalent organic frameworks (sCOFs) have attracted enormous interest for both fundamental research and application prospects. As the growth of sCOFs involves the assembly and reaction of precursors in a spatial defined manner, it is of great importance to understand the kinetics of sCOFs formation. Although several large families of sCOFs and bulk COF materials based on different coupling reactions have been reported, the synthesis of isomeric sCOFs by exchanging the coupling reaction moieties on precursors has been barely explored. Herein, a series of isomeric sCOFs based on Schiff-base reaction is designed to understand the effect of monomer structure on the growth kinetics of sCOFs. The distinctly different local packing motifs in the mixed assemblies for the two isomeric routes closely resemble to those in the assemblies of monomers, which affect the structural evolution process for highly ordered imine-linked sCOFs. In addition, surface diffusion of monomers and the molecule-substrate interaction, which is tunable by reaction temperature, also play an important role in structural evolutions. This study highlights the important roles of monomer structure and reaction temperature in the design and synthesis of covalent bond connected functional nanoporous networks.

The ordered array of nanovoids in nanoporous networks, such as honeycomb, Kagome, and square, provides a molecular template for the accommodation of “guest molecules”. Compared with the commonly studied guest molecules featuring high symmetry evenly incorporated into the template, guest molecules featuring lower symmetry are rare to report. Herein, we report the formation of a distinct patterned superlattice of guest molecules by selective trapping of guest molecules into the honeycomb network of trimesic acid (TMA). Two distinct surface patterns have been achieved by the guest inclusion induced adaptive reconstruction of a 2D molecular nanoporous network. The honeycomb networks can synergetically tune the arrangement upon inclusion of the guest molecules with different core size but similar peripherals groups, resulting in a trihexagonal Kagome or triangular patterns.

Two-dimensional (2D) nanomaterials, such as graphene and transition metal chalcogenides, show many interesting dimension-related materials properties. Inspired by the development of 2D inorganic nanomaterials, single-layered covalent organic frameworks (sCOFs), featuring atom-thick sheets and crystalline extended organic structures with covalently bonded building blocks, have attracted great attention in recent years. With their unique graphene-like topological structure and the merit of structural diversity, sCOFs promise to possess novel and designable properties. However, the synthesis of sCOFs with well-defined structures remains a great challenge. Herein, the recent development of the bottom-up synthesis methods of 2D sCOFs, such as thermodynamic equilibrium control methods, growth-kinetics control methods, and surface-assisted covalent polymerization methods, are reviewed. Finally, some of the critical properties and application prospects of these materials are outlined.

Preliminary studies with the four extracts of Oxytropis falcate Bunge exhibited that the chloroform and ethyl acetate extracts showed stronger antibacterial activities against the nine tested Gram-positive and Gram-negative bacteria. The HPLC-scanned and bioassay-guided fractionation led to the isolation and identification of the main flavonoid compounds, i.e. rhamnocitrin, kaempferol, rhamnetin, 2',4'-dihydroxychalcone and 2',4',beta-trihydroxy-dihydrochalcon. Except 2',4',beta-trihydroxy-dihydrochalcon, four other compounds had good antibacterial activities. The minimal inhibitory concentrations (MICs) and minimal bactericidal concentrations (MBCs) of the four compounds ranged between 125 and 515 microg mL(-1). Staphylococcus aureus was the most susceptible to these compounds, with MIC and MBC values from 125 to 130 microg mL(-1). This is the first report of antibacterial activity in O. falcate Bunge. In this study, evidence to evaluate the biological functions of O. falcate Bunge is provided, which promote the rational use of this herb.