Polyoxometallate Cluster Induced High-Entropy Oxide Sub-1 nm Nanosheets as Photoelectrocatalysts for Zn-Air Batteries.

The lack of highly efficient and inexpensive catalysts severely hinders the large-scale application of Zn-air batteries (ZABs). High-entropy oxides (HEOs) exhibit unique structures and attractive properties; thus, they are promising to be used in ZABs. However, conventional high-temperature synthesis methods tend to obtain microscale HEOs with a lower exposure rate of active sites. Here, we report a facile solvothermal strategy for preparing two-dimensional (2D) HEO sub-1 nm nanosheets (SNSs) induced by polyoxometalate (POM) clusters. Taking advantage of the special 2D sub-1 nm structure and precise element regulation, these 2D HEOs-POM SNSs exhibit enhanced bifunctional oxygen evolution and oxygen reduction reaction activity under light irradiation. Further applying these 2D HEOs-POM SNSs to ZABs as cathode catalysts, the CoFeNiMnCuZnOx-phosphomolybdic acid SNSs-based ZABs deliver a low charge/discharge voltage gap of 0.25 V at 2 mA cm-2 under light irradiation. Meanwhile, it could maintain an ultralong-term stability for 1600 h at 2 mA cm-2 and 930 h at 10 mA cm-2. The 2D sub-1 nm structure and fine element control in HEOs provide opportunities to solve the problems of low intrinsic activity, limited active sites, and instability of air cathodes in ZABs.

Tuning the Chirality Evolution in Achiral Subnanometer Systems by Judicious Control of Molecule Interactions.

Chirality evolution from molecule levels to the nanoscale in an achiral system is a fundamental issue that remains undiscovered. Here, we report the assembly of polyoxometalate (POM) clusters into chiral subnanostructures in achiral systems by programmable single-molecule interactions. Driven by the competing binding of Ca2+ and surface ligands, POM assemblies would twist into helical nanobelts, nanorings, and nanotubes with tunable helicity. Chiral molecules can be used to differentiate the formation energies of chiral isomers and immobilize the homochiral isomer, where strong circular dichroism (CD) signals are obtained in both solutions and films. Chiral helical nanobelts can be used as circularly polarized light (CPL) photodetectors due to their distinct chiroptic responsivity for right and left CPL. By the fine-tuning of interactions at single-molecule levels, the morphology and CD spectra of helical assemblies can be precisely controlled, providing an atomic precision model for investigation of the structure-chirality relationship and chirality manipulation at the nanoscale.

Single-Walled Cluster Nanotubes for Single-Atom Catalysts with Precise Structures.

Spatially confining isolated atomic sites in low-dimensional nanostructures is a promising strategy for preparing high-performance single-atom catalysts (SACs). Herein, fascinating polyoxometalate cluster-based single-walled nanotubes (POM-SWNTs) with atomically precise structures, uniform diameter, and single-cluster wall thickness are constructed by lacunary POM clusters (PW11 and P2W17 clusters). Isolated metal centers are accurately incorporated into the PW11-SWNTs and P2W17-SWNTs supports. The structures of the resulting MPW11-SWNTs and MP2W17-SWNTs are well established (M = Cu, Pt). Molecular dynamics simulations demonstrate the stability of POM-SWNTs. Furthermore, the turnover frequency of PtP2W17-SWNTs is 20 times higher than that of PtP2W17 cluster units and 140 times higher than that of Pt nanoparticles in the alcoholysis of dimethylphenylsilane. Theoretical studies indicate that incorporating a Pt atom into the P2W17 support induces straightforward electron transfer between them, combining the nanoconfined environment to enhance the catalytic activity of PtP2W17-SWNTs. This work shows the feasibility of using subnanometric POM clusters to assemble single-walled cluster nanotubes, highlighting their potential to prepare superior SACs with precise structures.

Sub-Nanosheet Induced Inverse Growth of Negative Valency Au Clusters for Tumor Treatment by Enhanced Oxidative Stress.

Cluster aggregation states are thermodynamically favored at the subnanoscale, for which an inverse growth from nanoparticles to clusters may be realized on subnanometer supports. Herein, we develop Au-polyoxometalate-layered double hydroxide (Au-POM-LDH) sub-1 nm nanosheets (Sub-APL) based on the above strategy, where sub-1 nm Au clusters with negative valence are generated by the in-situ disintegration of Au nanoparticles on POM-LDH supports. Sub-1 nm Au clusters with ultrahigh surface atom ratios exhibit remarkable efficiency for glutathione (GSH) depletion. The closely connected sub-1 nm Au with negative valence and POM hetero-units can promote the separation of hole-electrons, resulting in the enhanced reactive oxygen species (ROS) generation under ultrasound (US). Besides, the reversible redox of Mo in POM is able to deplete GSH and trigger chemodynamic therapy (CDT) simultaneously, further enhancing the oxidative stress. Consequently, the Sub-APL present 2-fold ROS generation under US and 7-fold GSH depletion compared to the discrete Au and POM-LDH mixture. Therefore, the serious imbalance of redox in the TME caused by the sharp increase of ROS and rapid decrease of GSH leads to death of tumor ultimately.

Photoluminescence Quenching of Hydrophobic Ag29 Nanoclusters Caused by Molecular Decoupling during Aqueous Phase Transfer and EmissionRecovery through Supramolecular Recoupling.

Exploiting emissive hydrophobic nanoclusters for hydrophilic applications remains a challenge because of photoluminescence (PL) quenching during phase transfer. In addition, the mechanism underlying PL quenching remains unclear. In this study, the PL-quenching mechanism was examined by analyzing the atomically precise structures and optical properties of a surface-engineered Ag29 nanocluster with an all-around-carboxyl-functionalized surface. Specifically, phase-transfer-triggered PL quenching was justified as molecular decoupling, which directed an unfixed cluster surface and weakened the radiative transition. Furthermore, emission recovery of the quenched nanoclusters was accomplished by using a supramolecular recoupling approach through the glutathione-addition-induced aggregation of cluster molecules, wherein the restriction of intracluster motion and intercluster rotation strengthened the radiative transition of the clusters. The results of this work offer a new perspective on structure-emission correlations for atomically precise nanoclusters and hopefully provide insight into the fabrication of highly emissive cluster-based nanomaterials for downstream hydrophilic applications.

Single-cluster Functionalized TiO2 Nanotube Array for Boosting Water Oxidation and CO2 Photoreduction to CH3OH.

Solar-driven CO2 reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CH3OH and CH3CH2OH dominated by multi-electron transfer. Single-cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge. Herein, we develop a facile electrosynthesis method to uniformly disperse Wells-Dawson- and Keggin-type polyoxometalates on TiO2 nanotube arrays, resulting in a series of single-cluster functionalized catalysts P2M18O62@TiO2 and PM12O40@TiO2 (M=Mo or W). The single polyoxometalate cluster can be distinctly identified and serves as electronic sponge to accept electrons from excited TiO2 for enhancing surface-hole concentration and promote water oxidation. Among these samples, P2Mo18O62@TiO2-1 exhibits the highest electron consumption rate of 1260 µmol g-1 for CO2-to-CH3OH conversion with H2O as the electron source, which is 11 times higher than that of isolated TiO2 nanotube arrays. This work supplied a simple synthesis method to realize the single-dispersion of molecular cluster to enrich surface-reaching holes on TiO2, thereby facilitating water oxidation and CO2 reduction.

SERS Detection of Trace Carcinogenic Aromatic Amines Based on Amorphous MoO3 Monolayers.

Aromatic amines are important commercial chemicals, but their carcinogenicity poses a threat to humans and other organisms, making their rapid quantitative detection increasingly urgent. Here, amorphous MoO3 (a-MoO3) monolayers with localized surface plasmon resonance (LSPR) effect in the visible region are designed for the trace detection of carcinogenic aromatic amine molecules. The hot-electron fast decay component of a-MoO3 decreases from 301 fs to 150 fs after absorption with methyl orange (MO) molecules, indicating the plasmon-induced hot-electron transfer (PIHET) process from a-MoO3 to MO. Therefore, a-MoO3 monolayers present high SERS performance due to the synergistic effect of electromagnetic enhancement (EM) and PIHET, proposing the EM-PIHET synergistic mechanism in a-MoO3. In addition, a-MoO3 possesses higher electron delocalization and electronic state density than crystal MoO3 (c-MoO3), which is conducive to the PIHET. The limit of detection (LOD) for o-aminoazotoluene (o-AAT) is 10-9 M with good uniformity, acid resistance, and thermal stability. In this work, trace detection and identification of various carcinogenic aromatic amines based on a-MoO3 monolayers is realized, which is of great significance for reducing cancer infection rates.

Building Co16-N3-Based UiO-MOF to Expand Design Parameters for MOF Photosensitization.

The construction of secondary building units (SBUs) in versatile metal-organic frameworks (MOFs) represents a promising method for developing multi-functional materials, especially for improving their sensitizing ability. Herein, we developed a dual small molecules auxiliary strategy to construct a high-nuclear transition-metal-based UiO-architecture Co16-MOF-BDC with visible-light-absorbing capacity. Remarkably, the N3 - molecule in hexadecameric cobalt azide SBU offers novel modification sites to precise bonding of strong visible-light-absorbing chromophores via click reaction. The resulting Bodipy@Co16-MOF-BDC exhibits extremely high performance for oxidative coupling benzylamine (~100 % yield) via both energy and electron transfer processes, which is much superior to that of Co16-MOF-BDC (31.5 %) and Carboxyl @Co16-MOF-BDC (37.5 %). Systematic investigations reveal that the advantages of Bodipy@Co16-MOF-BDC in dual light-absorbing channels, robust bonding between Bodipy/Co16 clusters and efficient electron-hole separation can greatly boost photosynthesis. This work provides an ideal molecular platform for synergy between photosensitizing MOFs and chromophores by constructing high-nuclear transition-metal-based SBUs with surface-modifiable small molecules.

Quantitatively Unveiling the Structure-Activity Relationship of Polyamide Nanofiltration Membranes with Complex Structures.

Nanofiltration polyamide (NF PA) membranes are widely used in seawater desalination and wastewater treatment due to their excellent permeability. The structure-activity relationship of PA membranes has attracted extensive attention in decades. In this work, NF PA membranes with planar structure, nodular structure, and peak-valley structure were constructed, and the pure water permeance was calculated by nonequilibrium molecular dynamics simulation to quantitatively investigate the structure-activity relationship between the microstructure and water permeance. Results showed that the peak-valley structure had the highest effective utilization rate of the membrane surface, which had the highest number of water molecules that passed through membranes per unit cross-sectional area (7.09). Furthermore, with the increase of the specific surface area ratio, the water permeance of the NF PA with peak-valley increased at a rate about 2.5 times than that of the planar NF PA. Therefore, some molecular scale insights were supplied about the structure-activity relationship of NF PA membranes, which is helpful for the fabrication of high-performance NF PA membranes.

Graphene Oxide-Mediated Synthesis of Ultrathin Co-MOL for CO2 Photoreduction.

Metal-organic framework (MOF) materials have broad application prospects in catalysis because of their ordered structure and molecular adjustability. However, the large volume of bulky MOF usually leads to insufficient exposure of the active sites and the obstruction of charge/mass transfer, which greatly limits their catalytic performance. Herein, we developed a simple graphene oxide (GO) template method to fabricate ultrathin Co-metal-organic layer (2.0 nm) on reduced GO (Co-MOL@r-GO). The as-synthesized hybrid material Co-MOL@r-GO-2 exhibits highly efficient photocatalytic performance for CO2 reduction, and the CO yield can reach as high as 25,442 µmol/gCo-MOL, which is over 20 times higher than that of the bulky Co-MOF. Systematic investigations demonstrate that GO can act as a template for the synthesis of the ultrathin Co-MOL with more active sites and can be used as the electron transport medium between the photosensitizer and the Co-MOL to enhance the catalytic activity for CO2 photoreduction.

Hybrid Sub-1 nm Nanosheets of Co-assembled MnZnCuOx and Polyoxometalate Clusters as Anodes for Li-ion Batteries.

Transition metal oxide (TMO) anode materials in lithium-ion batteries (LIBs) usually suffer from serious volume expansion leading to the pulverization of structures, further giving rise to lower specific capacity and worse cycling stability. Herein, by introducing polyoxometalate (POM) clusters into TMOs and precisely controlling the amount of POMs, the MnZnCuOx -phosphomolybdic acid hybrid sub-1 nm nanosheets (MZC-PMA HSNSs) anode is successfully fabricated, where the special electron rich structure of POMs is conducive to accelerating the migration of lithium ions on the anode to obtain higher specific capacity, and the non-covalent interactions between POMs and TMOs make the HSNSs possess excellent structural and chemical stability, thus exhibiting outstanding electrochemical performance in LIBs, achieving a high reversible capacity (1157 mAh g-1 at 100 mA g-1 ) and an admirable long-term cycling stability at low and high current densities.

Regulating the Mechanical and Optical Properties of Polymer-based Nanocomposites by Sub-Nanowires.

Sub-nanowires (SNWs) exhibit great potential applications in nanocomposites owing to their high specific surface area, high flexibility, and similarity to polymer chains in dimension, which are a good entry point to bridge inorganic materials and polymer materials. Herein, we synthesized hydroxyapatite sub-nanowires (HAP SNWs) and engineered hydroxyapatite sub-nanowires/polyimide (HSP) gels and films by simple mixing of HAP SNWs and polyimide (PI). Benefiting from the interactions between HAP SNWs and PI, these nanocomposites were a continuous hybrid network. As the increase of HAP SNWs contents, the viscosity and modulus of HSP gels were greatly improved by one or two orders of magnitude compared with PI gel. HSP films not only maintained high transparency but also gained high haze, as well as exhibited enhanced Young's modulus. Thus, both HSP gels and films developed in this work are promising for various applications in coatings and high-performance films.

Interfacial Self-assembly of Chiral Selenide Nanomembrane for Enantiospecific Recognition.

Here, we report the synthesis of chiral selenium nanoparticles (NPs) using cysteine and the interfacial assembly strategy to generate a self-assembled nanomembrane on a large-scale with controllable morphology and handedness. The selenide (Se) NPs exhibited circular dichroism (CD) bands in the ultraviolet and visible region with a maximum intensity of 39.96 mdeg at 388 nm and optical anisotropy factors (g-factors) of up to 0.0013 while a self-assembled monolayer nanomembrane exhibited symmetrical CD approaching 72.8 mdeg at 391 nm and g-factors up to 0.0034. Analysis showed that a photocurrent of 20.97±1.55 nA was generated by the D-nanomembrane when irradiated under light while the L-nanomembrane generated a photocurrent of 20.58±1.36 nA. Owing to the asymmetric intensity of the photocurrent with respect to the handedness of the nanomembrane, an ultrasensitive recognition of enantioselective kynurenine (Kyn) was achieved by the ten-layer (10L) D-nanomembrane exhibiting a photocurrent for L-kynurenine (L-Kyn) that was 8.64-fold lower than that of D-Kyn, with a limit of detection (LOD) of 0.0074 nM for the L-Kyn, which was attributed to stronger affinity between L-Kyn and D-Se NPs. Noticeably, the chiral Se nanomembrane precisely distinguished L-Kyn in serum and cerebrospinal fluid samples from Alzheimer's disease patients and healthy subjects.

Self-Assembly of Polyoxometalate-Based Sub-1†nm Polyhedral Building Blocks into Rhombic Dodecahedral Superstructures.

Self-assembly of subnanometer (sub-1 nm) scale polyhedral building blocks can yield some superstructures with novel and interesting morphology as well as potential functionalities. However, achieving the self-assembly of sub-1 nm polyhedral building blocks is still a great challenge. Herein, through encapsulating the titanium-substituted polyoxometalate (POM, K7 PTi2 W10 O40 ) with tetrabutylammonium cations (TBA+ ), we first synthesized a sub-1 nm rhombic dodecahedral building block by further tailoring the spatial distribution of TBA+ on the POM. Molecular dynamics (MD) simulations demonstrated the eight TBA+ cations interacted with the POM cluster and formed the sub-1 nm rhombic dodecahedron. As a result of anisotropy, the sub-1 nm building blocks have self-assembled into rhombic dodecahedral POM (RD-POM) assemblies at the microscale. Benefiting from the regular structure, Br- ions, and abundant active sites, the obtained RD-POM assemblies exhibit excellent catalytic performance in the cycloaddition of CO2 with epoxides without co-catalysts. This work provides a promising approach to tailor the symmetry and structure of sub-1 nm building blocks by tuning the spatial distribution of ligands, which may shed light on the fabrication of superstructures with novel properties by self-assembly.

Versatile Inorganic Subnanometer Nanowire Adhesive.

Adhesives are applied extensively in daily life and industries, and people have developed numerous commercial polymeric adhesives. However, in most cases, these adhesives work on dry surfaces in air and form permanent bonds with the substrates, limiting the applications of adhesives. Inspired by the innate adhesive functions of some animals, such as geckos, spiders, mussels, and clingfish, scientists have developed various adhesive compositions and structures to meet various conditions. Here, we show a versatile subnanometer nanowire (SNW) adhesive with high strength and great reversibility, which could be prepared at a large scale through a facile room-temperature reaction. The SNW adhesive contacts the substrates at multiple sites due to the ultrahigh flexibility, and meanwhile, the multilevel interactions among the SNWs endow them with strong cohesion, so they exhibit good adhesive performance. This adhesive is applicable to various substrates, such as metals, polymers, and glass, and not only possesses good stability at room temperature in air but also is suitable for underwater environments and ultralow temperatures. Moreover, this adhesive could be easily recycled and removed from the substrates without any residue and damage. The SNW adhesive not only inspires the design of hierarchical adhesive structures with new contact modes but also has potential for practical applications.

Polyoxometalate Cluster-Incorporated High Entropy Oxide Sub-1 nm Nanowires.

High entropy oxides (HEOs) with fascinating physical and chemical properties have exhibited unprecedented application potential in many fields. However, it remains a huge challenge to realize the precise control of the dimension and morphology at the sub-1 nm scale. Herein, with the aid of polyoxometalate (POM) clusters, we first develop a versatile strategy to realize the controllable incorporation of multiple immiscible metal oxides into sub-1 nm nanowires (SNWs) under 140 °C to obtain a wide range of HEO-POM SNWs with highly ordered structures, where the species of metal oxides and POMs could be regulated flexibly. Meanwhile, these obtained HEO materials are first to be used as anodes in Na-ion batteries. Benefiting from the effect of entropy modulation, these HEO-POM SNWs show better electrochemical properties in Na-ion batteries with the increase of metal oxide species stepwise. A long cycle life with a capacity retention of ∼92% even after 5000 cycles at 10C further confirms the good stability under fast discharging/charging. This method opens a new insight for designing and preparing HEOs at the sub-1 nm scale under facile conditions.

Graphene oxide membranes with a confined mass transfer effect for Li+/Mg2+ separation: a molecular dynamics study.

Membrane separation technology represented by graphene oxide (GO) membranes has been widely used in lithium extraction from salt lakes. It is extraordinary to study the extraction of Li+ by GO membranes from the perspective of the confined mass transfer effect. This study establishes a GO channel model with the confined mass transfer effect to closely fit the actual mass transfer process. Meanwhile, this study investigates the dynamic fluid characteristics in the separation of Li+/Mg2+ by GO membranes using molecular dynamics simulations. The results showed that the Li+/Mg2+ separation ratio is maximum at 1.0 nm layer spacing and 10% oxidation degree of the GO membrane. Water molecules form a bilayer within the channel at the appropriate interlayer channel (1 nm) and oxidation level (10%), which accelerates the ion transport rate. Furthermore, the GO oxidation group has the weakest hydrogen bonding effect on water which promotes the passage of water. Finally, the maximum separation ratio is reached due to the fact that the binding force of Li+ to water molecules in the channel is lower than that of Mg2+. The results of this study will provide theoretical consideration for the design of high-performance Li+/Mg2+ separation membranes.

Circularly and Linearly Polarized Luminescence from AIE Luminogens Induced by Super-Aligned Assemblies of Sub-1†nm Nanowires.

Sub-1 nm nanowires (SNWs) combine the properties of inorganic materials and polymers. They can be highly oriented through assembly, and can also be easily processed. Meanwhile, aggregation-induced emission luminogens (AIEgens) show high potential for optical applications, but they are usually hard to process. The combination of SNWs and AIEgens can enrich both of their applications. In this study, we report that the fluorescence emission intensity of the AIEgens-SNW dispersion is dramatically enhanced due to the flexibility of SNWs. Furthermore, we fabricate two kinds of functional films with circularly polarized luminescence (CPL) and linearly polarized luminescence (LPL) activities. The construction of CPL materials didn't require any chiral chemicals. The construction of LPL materials didn't require an additional stretching process. As a result, we endowed common achiral AIEgens with a high dissymmetry factor of 0.033 and a polarization ratio of 0.44, respectively.

ZnO-POM Cluster Sub-1 nm Nanosheets as Robust Catalysts for the Oxidation of Thioethers at Room Temperature.

Two-dimensional (2D) zinc oxides have attracted more and more research interests due to their unique properties. Yet, it remains a great challenge to limit the thickness to the sub-1 nm scale and further combine with other components to obtain 2D hybrid zinc oxide (ZnO)-based sub-1 nm materials. Herein, a versatile strategy was successfully developed to realize the controllable preparation of ZnO-polyoxometalate (POM)-based 2D hybrid sub-1 nm nanosheet (HSNS) superstructures by incorporating three kinds of molybdenum-based POM clusters into the zinc oxide system. Molecular dynamics simulation results demonstrated that POM clusters interact with ZnO/Zn(OH)2 molecules and coassembled into stable 2D HSNSs. Significantly, theses materials as robust catalysts showed excellent catalytic activity, selectivity, and stability in the oxidation of thioethers at room temperature, which partly can be attributed to the special 2D sub-1 nm nanostructures with large specific areas leading to the full exposure of active sites. Meanwhile, the synergetic effect of multiple components also played an important role during the catalytic process. Thus, this work would pave the way for the precise synthesis of multicomponent 2D hybrid sub-1 nm materials for widespread applications.

Modifiers versus Channels: Creating Shape-Selective Catalysis of Metal Nanoparticles/Porous Nanomaterials.

Shape-selective catalysis plays a key role in chemical synthesis. Porous nanomaterials with uniform pore structures are ideal supports for metal nanoparticles (MNPs) to generate efficient shape-selective catalysis. However, many commercial irregular porous nanomaterials face the challenge to realize satisfactory shape selectivity due to the lack of molecular sieving structures. Herein, we report a concept of creating shape selectivity in MNPs/porous nanomaterials through intentionally poisoning certain MNPs using suitable modifiers. The remaining MNPs within the substrates can cooperate with the channels to generate selectivity. Such a strategy not only applies to regular porous nanomaterials (such as MOFs, zeolites) but also extended to irregular porous nanomaterials (such as active carbon, P25). Potentially, the matching among different MNPs, corresponding modifiers, and porous nanomaterials makes our strategy promising in selective catalytic systems.