Low Loading and High Activity of Platinum Oxide Nanoclusters Formed by Defect Engineering of a Metal-Organic Framework for Formaldehyde Degradation.

A distinct platinum oxide nanocluster (PtOx ) was developed, consisting of only Pt-O bond by a defect-engineered Al metal-organic framework (MOF) (BIT-72) with superior formaldehyde (HCHO) degradation activity and stability. With only 0.015 wt % Pt loading, PtOx @BIT-72-DE could degrade HCHO with 100 % conversion continuously for at least 200 h under HCHO concentration of 25 ppm and gas hourly space velocity of 60000 mL g-1 h-1 at room temperature. Furthermore, its specific rate (446 mmolHCHO gPt -1 h-1 ) was higher than for traditional Pt-based catalysts and single-atom Pt catalysts. Moreover, the cost of PtOx @BIT-72-DE was lowered to 0.0769 $ g-1 , which could significantly facilitate its commercial application. This study demonstrates the promising potential of MOFs in the design of HCHO degradation catalysts.

General Synthesis of Ordered Mesoporous Carbonaceous Hybrid Nanostructures with Molecularly Dispersed Polyoxometallates.

Hybrid nanomaterials with controlled dimensions, intriguing components and ordered structures have attracted significant attention in nanoscience and technology. Herein, we report a facile and green polyoxometallate (POM)-assisted hydrothermal carbonization strategy for synthesis of carbonaceous hybrid nanomaterials with molecularly dispersed POMs and ordered mesopores. By using various polyoxometallates such as ammonium phosphomolybdate, silicotungstic acid, and phosphotungstic acid, our approach can be generalized to synthesize ordered mesoporous hybrid nanostructures with diverse compositions and morphologies (nanosheet-assembled hierarchical architectures, nanospheres, and nanorods). Moreover, the ordered mesoporous nanosheet-assembled hierarchical hybrids with molecularly dispersed POMs exhibit remarkable catalytic activity toward the dehydration of tert-butanol with the high isobutene selectivity (100 %) and long-term catalytic durability (80 h).

Preparation of CdSy Se1- y -MoS2 Heterostructures via Cation Exchange of Pre-Epitaxially Synthesized Cu2- χ Sy Se1- y -MoS2 for Photocatalytic Hydrogen Evolution.

Construction of 2D transition metal dichalcogenide (TMD)-based epitaxial heterostructures with different compositions is important for various promising applications, including electronics, photonics, and catalysis. However, the rational design and controlled synthesis of such kind of heterostructures still remain challenge, especially for those consisting of layered TMDs and other non-layered materials. Here, a facile one-pot, wet-chemical method is reported to synthesize Cu2- χ Sy Se1- y -MoS2 heterostructures in which two types of different epitaxial configurations, i.e., vertical and lateral epitaxies, coexist. The chalcogen ratio (S/Se) in Cu2- χ Sy Se1- y and the loading amount of MoS2 in the heterostructures can be tuned. Impressively, the obtained Cu2- χ Sy Se1- y -MoS2 heterostructures can be transformed to CdSy Se1- y -MoS2 without morphological change via cation exchange. As a proof-of-concept application, the obtained CdSy Se1- y -MoS2 heterostructures with controllable compositions are used as photocatalysts, exhibiting distinctive catalytic activities toward the photocatalytic hydrogen evolution under visible light irradiation. The method paves the way for the synthesis of different TMD-based lateral epitaxial heterostructures with unique properties for various applications.

Rational Design of MOF-Based Hybrid Nanomaterials for Directly Harvesting Electric Energy from Water Evaporation.

The continuous exploration of clean-energy technology is critical for the sustainable development of society. The recent work on the electric energy harvesting from water evaporation has made a significant contribution to the utilization of clean energy for self-powering systems. Here, a novel metal-organic-framework-based hybrid nanomaterial is delicately designed and synthesized by the growth of UIO-66 nanoparticles on 2D AlOOH nanoflakes. Due to the combined merits from the 2D morphology, which is inherited from the AlOOH nanoflakes, and the high surface potential, which originates from the UIO-66 nanoparticles, the device made of the AlOOH/UIO-66 hybrid nanomaterials can harvest electric energy from natural water evaporation. An open-circuit voltage of 1.63 ± 0.10 V can be achieved on the prototype devices made of the hybrid nanomaterial. As a proof-of-concept application, a small electric appliance, e.g., a digital calculator, is powered up by a 3 × 3 device array connected in a combined series-parallel configuration.

Transition metal dichalcogenide/multi-walled carbon nanotube-based fibers as flexible electrodes for electrocatalytic hydrogen evolution.

We report a general strategy for the fabrication of binder-free, flexible and weavable transition-metal dichalcogenide nanosheet-based hybrid fibers by using well-aligned multi-walled carbon nanotubes as hosts. The resulting hybrid fibers are used as electrodes for electrocatalytic hydrogen evolution, showing excellent performance in both acidic and basic environments, and excellent long-term stability.

Synthesis of Palladium-Based Crystalline@Amorphous Core-Shell Nanoplates for Highly Efficient Ethanol Oxidation.

Phase engineering of nanomaterials (PEN) offers a promising route to rationally tune the physicochemical properties of nanomaterials and further enhance their performance in various applications. However, it remains a great challenge to construct well-defined crystalline@amorphous core-shell heterostructured nanomaterials with the same chemical components. Herein, the synthesis of binary (Pd-P) crystalline@amorphous heterostructured nanoplates using Cu3- χ P nanoplates as templates, via cation exchange, is reported. The obtained nanoplate possesses a crystalline core and an amorphous shell with the same elemental components, referred to as c-Pd-P@a-Pd-P. Moreover, the obtained c-Pd-P@a-Pd-P nanoplates can serve as templates to be further alloyed with Ni, forming ternary (Pd-Ni-P) crystalline@amorphous heterostructured nanoplates, referred to as c-Pd-Ni-P@a-Pd-Ni-P. The atomic content of Ni in the c-Pd-Ni-P@a-Pd-Ni-P nanoplates can be tuned in the range from 9.47 to 38.61 at%. When used as a catalyst, the c-Pd-Ni-P@a-Pd-Ni-P nanoplates with 9.47 at% Ni exhibit excellent electrocatalytic activity toward ethanol oxidation, showing a high mass current density up to 3.05 A mgPd -1 , which is 4.5 times that of the commercial Pd/C catalyst (0.68 A mgPd -1 ).

Selective Epitaxial Growth of Oriented Hierarchical Metal-Organic Framework Heterostructures.

Metal-organic framework (MOF) heterostructures have shown promising applications in gas adsorption, gas separation, catalysis, and energy, arising from the synergistic effect of each component. However, owing to the difficulty in controlling the size, shape, nucleation, and growth of MOFs, it remains a great challenge to construct MOF heterostructures with precisely controlled orientation, morphology, dimensionality, and spatial distribution of each component. Here, we report a seeded epitaxial growth method to prepare a series of hierarchical MOF heterostructures by engineering the structures, sizes, dimensionalities, morphologies, and lattice parameters of both MOF seeds and the secondary MOFs. In these heterostructures, PCN-222 (also known as MOF-545) nanorods selectively grow along the major axis of the ellipsoid-like PCN-608 nanoparticles, on the two end facets of the hexagonal prism-like NU-1000 nanorods, and on the two basal planes of the hexagonal PCN-134 nanoplates, while Zr-BTB nanosheets selectively grow on the six edge facets of PCN-134 nanoplates. The selective epitaxial growth of MOFs opens the way to synthesize different hierarchical heterostructures with tunable architectures and dimensionalities, which could process various promising applications.

MOF-Based Hierarchical Structures for Solar-Thermal Clean Water Production.

Solar-thermal water evaporation, as a promising method for clean water production, has attracted increasing attention. However, solar water evaporators that exhibit both high water vapor generation ability and anti-oil-fouling ability have not been reported. Here, a unique metal-organic-framework-based hierarchical structure, referred to as MOF-based hierarchical structure (MHS), is rationally designed and prepared, which simultaneously displays a high solar absorption and a superhydrophilic and underwater superoleophobic surface property. As a proof-of-concept application, a device prepared from the MHS can achieve a high solar-thermal water evaporation rate of 1.50 kg m-2 h-1 under 1 sun illumination. Importantly, the MHS also possesses an excellent anti-oil-fouling property, ensuring its superior water evaporation performance even in oil-contaminated water. The high solar-thermal water evaporation rate and anti-oil-fouling property make the MHS a promising material for the solar-thermal water production.

Wet-Chemical Synthesis and Applications of Semiconductor Nanomaterial-Based Epitaxial Heterostructures.

Semiconductor nanomaterial-based epitaxial heterostructures with precisely controlled compositions and morphologies are of great importance for various applications in optoelectronics, thermoelectrics, and catalysis. Until now, various kinds of epitaxial heterostructures have been constructed. In this minireview, we will first introduce the synthesis of semiconductor nanomaterial-based epitaxial heterostructures by wet-chemical methods. Various architectures based on different kinds of seeds or templates are illustrated, and their growth mechanisms are discussed in detail. Then, the applications of epitaxial heterostructures in optoelectronics, catalysis, and thermoelectrics are described. Finally, we provide some challenges and personal perspectives for the future research directions of semiconductor nanomaterial-based epitaxial heterostructures.

A General Method for the Synthesis of Hybrid Nanostructures Using MoSe2 Nanosheet-Assembled Nanospheres as Templates.

The layered transition metal dichalcogenides (TMDs) and transition metal phosphides are low-cost, earth-abundant, and robust electrocatalysts for hydrogen evolution reaction (HER). Integrating them into hybrid nanostructures is potentially promising to further boost the catalytic activity toward HER based on their synergistic effects. Herein, we report a general method for the synthesis of a series of MoSe2-based hybrid nanostructures, including MoSe2-Ni2P, MoSe2-Co2P, MoSe2-Ni, MoSe2-Co, and MoSe2-NiS, by postgrowth of Ni2P, Co2P, Ni, Co, and NiS nanostructures on the presynthesized MoSe2 nanosheet-assembled nanospheres, respectively, via a colloidal synthesis method. As a proof-of-concept application, the as-synthesized hybrid nanostructures are used as electrocatalysts for HER, exhibiting high activity and stability in acidic media. Among them, the MoSe2-Co2P composite shows the highest HER activity with an overpotential of 167 mV at 10 mA cm-2.

Recent Progress in Graphene-Based Noble-Metal Nanocomposites for Electrocatalytic Applications.

The fast industrialization process has led to global challenges in the energy crisis and environmental pollution, which might be solved with clean and renewable energy. Highly efficient electrochemical systems for clean-energy collection require high-performance electrocatalysts, including Au, Pt, Pd, Ru, etc. Graphene, a single-layer 2D carbon nanosheet, possesses many intriguing properties, and has attracted tremendous research attention. Specifically, graphene and graphene derivatives have been utilized as templates for the synthesis of various noble-metal nanocomposites, showing excellent performance in electrocatalytic-energy-conversion applications, such as the hydrogen evolution reaction and CO2 reduction. Herein, the recent progress in graphene-based noble-metal nanocomposites is summarized, focusing on their synthetic methods and electrocatalytic applications. Furthermore, some personal insights on the challenges and possible future work in this research field are proposed.

Two-dimensional metal-organic framework nanosheets: synthesis and applications.

Two-dimensional (2D) metal-organic framework (MOF) nanosheets are attracting increasing research attention due to their unique properties originating from their ultrathin thickness, large surface area and high surface-to-volume atom ratios. Many great advances have been made in the synthesis and application of 2D MOF nanosheets over the past few years. In this review, we summarize the recent advances in the synthesis of 2D MOF nanosheets by using top-down methods, e.g. sonication exfoliation, mechanical exfoliation, Li-intercalation exfoliation and chemical exfoliation, and bottom-up methods, i.e. interfacial synthesis, three-layer synthesis, surfactant-assisted synthesis, modulated synthesis, and sonication synthesis. In addition, the recent progress in 2D MOF nanosheet-based nanocomposites is also briefly introduced. The potential applications of 2D MOF nanosheets in gas separation, energy conversion and storage, catalysis, sensors and biomedicine are discussed. Finally, we give our personal insights into the challenges and opportunities for the future research of 2D MOF nanosheets and their composites.

High phase-purity 1T'-MoS2- and 1T'-MoSe2-layered crystals.

Phase control plays an important role in the precise synthesis of inorganic materials, as the phase structure has a profound influence on properties such as conductivity and chemical stability. Phase-controlled preparation has been challenging for the metallic-phase group-VI transition metal dichalcogenides (the transition metals are Mo and W, and the chalcogens are S, Se and Te), which show better performance in electrocatalysis than their semiconducting counterparts. Here, we report the large-scale preparation of micrometre-sized metallic-phase 1T'-MoX2 (X = S, Se)-layered bulk crystals in high purity. We reveal that 1T'-MoS2 crystals feature a distorted octahedral coordination structure and are convertible to 2H-MoS2 following thermal annealing or laser irradiation. Electrochemical measurements show that the basal plane of 1T'-MoS2 is much more active than that of 2H-MoS2 for the electrocatalytic hydrogen evolution reaction in an acidic medium.

Novel structured transition metal dichalcogenide nanosheets.

Ultrathin two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have attracted considerable attention owing to their unique properties and great potential in a wide range of applications. Great efforts have been devoted to the preparation of novel-structured TMD nanosheets by engineering their intrinsic structures at the atomic scale. Until now, a lot of new-structured TMD nanosheets, such as vacancy-containing TMDs, heteroatom-doped TMDs, TMD alloys, 1T'/1T phase and in-plane TMD crystal-phase heterostructures, TMD heterostructures and Janus TMD nanosheets, have been prepared. These materials exhibit unique properties and hold great promise in various applications, including electronics/optoelectronics, thermoelectrics, catalysis, energy storage and conversion and biomedicine. This review focuses on the most recent important discoveries in the preparation, characterization and application of these new-structured ultrathin 2D layered TMDs.

Synthesis of WOn -WX2 (n=2.7, 2.9; X=S, Se) Heterostructures for Highly Efficient Green Quantum Dot Light-Emitting Diodes.

Preparation of two-dimensional (2D) heterostructures is important not only fundamentally, but also technologically for applications in electronics and optoelectronics. Herein, we report a facile colloidal method for the synthesis of WOn -WX2 (n=2.7, 2.9; X=S, Se) heterostructures by sulfurization or selenization of WOn nanomaterials. The WOn -WX2 heterostructures are composed of WO2.9 nanoparticles (NPs) or WO2.7 nanowires (NWs) grown together with single- or few-layer WX2 nanosheets (NSs). As a proof-of-concept application, the WOn -WX2 heterostructures are used as the anode interfacial buffer layer for green quantum dot light-emitting diodes (QLEDs). The QLED prepared with WO2.9 NP-WSe2 NS heterostructures achieves external quantum efficiency (EQE) of 8.53 %. To our knowledge, this is the highest efficiency in the reported green QLEDs using inorganic materials as the hole injection layer.

Growth of Au Nanoparticles on 2D Metalloporphyrinic Metal-Organic Framework Nanosheets Used as Biomimetic Catalysts for Cascade Reactions.

Inspired by the multiple functions of natural multienzyme systems, a new kind of hybrid nanosheet is designed and synthesized, i.e., ultrasmall Au nanoparticles (NPs) grown on 2D metalloporphyrinic metal-organic framework (MOF) nanosheets. Since 2D metalloporphyrinic MOF nanosheets can act as the peroxidase mimics and Au NPs can serve as artificial glucose oxidase, the hybrid nanosheets are used to mimic the natural enzymes and catalyze the cascade reactions. Furthermore, the synthesized hybrid nanosheets are used to detect biomolecules, such as glucose. This study paves a new avenue to design nanomaterial-based biomimetic catalysts with multiple complex functions.

Preparation of Superhydrophilic and Underwater Superoleophobic Nanofiber-Based Meshes from Waste Glass for Multifunctional Oil/Water Separation.

The deterioration of water resources due to oil pollution, arising from oil spills, industrial oily wastewater discharge, etc., urgently requires the development of novel functional materials for highly efficient water remediation. Recently, superhydrophilic and underwater superoleophobic materials have drawn significant attention due to their low oil adhesion and selective oil/water separation. However, it is still a challenge to prepare low-cost, environmentally friendly, and multifunctional materials with superhydrophilicity and underwater superoleophobicity, which can be stably used for oil/water separation under harsh working conditions. Here, the preparation of nanofiber-based meshes derived from waste glass through a green and sustainable route is demonstrated. The resulting meshes exhibit excellent performance in the selective separation of a wide range of oil/water mixtures. Importantly, these meshes can also maintain the superwetting property and high oil/water separation efficiency under various harsh conditions. Furthermore, the as-prepared mesh can remove water-soluble contaminants simultaneously during the oil/water separation process, leading to multifunctional water purification. The low-cost and environmentally friendly fabrication, harsh-environment resistance, and multifunctional characteristics make these nanofiber-based meshes promising toward oil/water separation under practical conditions.

Carbon-Based Functional Materials Derived from Waste for Water Remediation and Energy Storage.

Carbon-based functional materials hold the key for solving global challenges in the areas of water scarcity and the energy crisis. Although carbon nanotubes (CNTs) and graphene have shown promising results in various fields of application, their high preparation cost and low production yield still dramatically hinder their wide practical applications. Therefore, there is an urgent call for preparing carbon-based functional materials from low-cost, abundant, and sustainable sources. Recent innovative strategies have been developed to convert various waste materials into valuable carbon-based functional materials. These waste-derived carbon-based functional materials have shown great potential in many applications, especially as sorbents for water remediation and electrodes for energy storage. Here, the research progress in the preparation of waste-derived carbon-based functional materials is summarized, along with their applications in water remediation and energy storage; challenges and future research directions in this emerging research field are also discussed.

Anodized Aluminum Oxide Templated Synthesis of Metal-Organic Frameworks Used as Membrane Reactors.

The incorporation of metal-organic frameworks (MOFs) into membrane-shaped architectures is of great importance for practical applications. The currently synthesized MOF-based membranes show many disadvantages, such as poor compatibility, low dispersity, and instability, which severely limit their utility. Herein, we present a general, facile, and robust approach for the synthesis of MOF-based composite membranes through the in situ growth of MOF plates in the channels of anodized aluminum oxide (AAO) membranes. After being used as catalysis reactors, they exhibit high catalytic performance and stability in the Knoevenagel condensation reaction. The high catalytic performance might be attributed to the intrinsic structure of MOF-based composite membranes, which can remove the products from the reaction zone quickly, and prevent the aggregation and loss of catalysts during reaction and recycling process.

Self-Assembly of Single-Layer CoAl-Layered Double Hydroxide Nanosheets on 3D Graphene Network Used as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction.

A non-noble metal based 3D porous electrocatalyst is prepared by self-assembly of the liquid-exfoliated single-layer CoAl-layered double hydroxide nanosheets (CoAl-NSs) onto 3D graphene network, which exhibits higher catalytic activity and better stability for electrochemical oxygen evolution reaction compared to the commercial IrO2 nanoparticle-based 3D porous electrocatalyst.