Sub-1 nm Materials Chemistry: Challenges and Prospects.

Subnanometer materials (SNMs) refer to nanomaterials with a feature size close to 1 nm, similar to the diameter of a single polymer, DNA strand, and a single cluster/unit cell. The growth and assembly of subnanometer building blocks can be controlled by interactions at atomic levels, representing the limit for the precise manipulation of materials. The size, geometry, and flexibility of 1D SNMs inorganic backbones are similar to the polymer chains, bringing excellent gelability, adhesiveness, and processability different from inorganic nanocrystals. The ultrahigh surface atom ratio of SNMs results in significantly increased surface energy, leading to significant rearrangement of surface atoms. Unconventional phases, immiscible metal alloys, and high entropy materials with few atomic layers can be stabilized, and the spontaneous twisting of SNMs may induce the intrinsic structural chirality. Electron delocalization may also emerge at the subnanoscale, giving rise to the significantly enhanced catalytic activity. In this perspective, we summarized recent progress on SNMs, including their synthesis, polymer-like properties, metastable phases, structural chirality, and catalytic properties, toward energy conversion. As a critical size region in nanoscience, the development of functional SNMs may fuse the boundary of inorganic materials and polymers and conduce to the precise manufacturing of materials at atomic levels.

Entropy-Derived Synthesis of the CuPd Sub-1nm Alloy for CO2-to-acetate Electroreduction.

Bimetallic alloys exhibit remarkable properties in catalysis and energy storage, while their precise synthesis at the subnanoscale remains a formidable challenge due to their immiscible nature in thermodynamics. In this study, we engineer an atomically dispersed CuPd alloy with an average size of 1.5 nm loaded on CuO and phosphomolybdic acid (PMA) coassembly subnanosheets (CuO-PMA SNSs). Driven by the high vibrational entropy, Cu atoms could escape from CuO supports and bond with adjacent Pd single atoms, leading to the in situ formation of CuPd alloys. Furthermore, this strategy can also be utilized for synthesizing the ZnPt alloy with an average size of 1 nm, thereby providing a general pathway for the design of immiscible subnanoalloys. The fully exposed Cu-Pd pairs in CuPd subnanoalloys significantly enhance the adsorption and coverage of surface *CO during the electrochemical reduction of CO2, thereby leading to enhanced stability of ethenone intermediates and facilitating the production of C2 compounds. The resulting CuPd subnanoalloy exhibits a remarkable Faradaic efficiency of 46.5 ± 2.1% for CO2-to-acetate electroreduction and achieves a high acetate productivity of 99 ± 2.8 µmol cm-2 at -0.7 V versus RHE.

Active Learning Guided Discovery of High Entropy Oxides Featuring High H2-production.

High entropy oxides (HEOs) represent a class of solid solutions comprising multiple elements, offering significant scientific potential. Due to the enormous combination types of elements, the design of HEOs with desirable properties within high-dimensional composition spaces has traditionally relied heavily on knowledge and intuition. In this study, we present an active learning (AL) strategy tailored to efficiently explore the vast compositional space of HEOs. Our approach operates as a closed-loop system, iteratively cycling through "Training, Prediction, and Experiment" stages. Across multiple AL iterations, we have successfully identified four novel HEOs from a vast array of potential compositions. These newly discovered materials exhibit exceptional stability and demonstrate outstanding performance in H2 evolution rate (251 µmol gcat-1 min-1) during the water-gas shift reaction, surpassing benchmarks set by established catalysts such as Pt/γ-Al2O3 (135 µmol gcat-1 min-1) and Cu/ZnO/Al2O3 (81 µmol gcat-1 min-1). X-ray photoelectron spectroscopy and density functional theory calculations revealed a loss of elemental identity in the selected HEOs. This catalyst discovery process underscores the efficacy of Machine Learning in accelerating the identification of HEOs with unique characteristics by effectively leveraging insights from limited experimental data.

Activating and Stabilizing Lattice Oxygen via Self-Adaptive Zn-NiOOH Sub-Nanowires for Oxygen Evolution Reaction.

Efficient and durable catalysts for the oxygen evolution reaction are essential for realizing the large-scale application of water electrolysis technologies. Here, we report a novel Zn-doped NiOOH subnanowires (Zn-NiOOH SNWs) catalyst synthesized via the electrochemical reconstruction of Zn-NiMoO4 SNWs. The inclusion of Zn triggers a transition in the oxygen evolution reaction mechanism of NiOOH from the adsorbate evolution mechanism to the lattice oxygen mechanism, resulted from Zn's adaptive adjustment of coordination types, which also improves the reaction energetics, thereby enhancing the stability and activity. Furthermore, the subnanowire structure provides further stabilization of the lattice oxygen in Zn-NiOOH, preventing its destructive dissolution. Remarkably, Zn-NiOOH SNWs display a current density of 10 mA cm-2 with an overpotential of only 179 mV and maintain stable operation at 200 mA cm-2 for 800 h with minimal changes in overpotential, establishing them as one of the most effective catalysts involving lattice oxygen for the alkaline oxygen evolution reaction. When utilized as the anode in an alkaline water electrolyzer, our Zn-NiOOH SNWs catalyst demonstrates stability exceeding 500 h under a water-splitting current of 200 mA cm-2, indicating promising potential for practical applications.

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.

Electron-Delocalization Across High Surface Entropy Sub-1 nm Nanobelts Toward Enhanced Electrocatalytic Urea Oxidation.

Integration of inherently incompatible elements into a single sublattice, resulting in the formation of monophasic metal oxide, holds great scientific promise; it unveils that the overlooked surface entropy in subnanometer materials can thermodynamically facilitate the formation of homogeneous single-phase structures. Here a facile approach is proposed for synthesizing multimetallic oxide subnanometer nanobelts (MMO-PMA SNBs) by harnessing the potential of phosphomolybdic acid (PMA) clusters to capture inorganic nuclei and inhibiting their subsequent growth in solvothermal reactions. Experimental and theoretical analyses show that PMA in MMO-PMA SNBs not only aids subnanometer structure formation but also induces in situ modifications to catalytic sites. The electron transfer from PMA, coupled with the loss of elemental identity of transition metals, leads to electron delocalization, jointly activating the reaction sites. The unique structure makes pentametallic oxide (PMO-PMA SNBs) achieve a current density of 10 mA cm-2 at a low potential of 1.34 V and remain stable for 24 h at 10 mA cm-2 on urea oxidation reaction (UOR). The exceptional UOR catalytic activity suggests a potential for utilizing multimetallic subnanometer nanostructures in energy conversion and environmental remediation.

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.

Precise Assembly of Polyoxometalates at Single-cluster Levels.

Polyoxometalate (POM) clusters with atomic precision structures are promising candidates construct functional nanomaterials via self-assembly. Non-covalent interactions at molecular levels can govern the self-assembly of POM clusters, for which the precise control of POM-based assemblies can be realized at single-cluster levels. This mini-review focuses on the synthesis and properties of POM-based nanostructures, including amphiphilic POM assemblies and co-assemblies of POM clusters and other subnanometer building blocks. Several synthetic strategies have been developed for rational control of POM-based assemblies in terms of morphologies, compositions and properties. 1D subnanometer POM assemblies demonstrate remarkable enhanced mechanical properties due to the topological interactions between nanowires and surroundings. The in-depth understanding of POM-based assemblies may help in the design of functional nanomaterials in fundamental perspectives and applications.

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.

Polyoxometalate Induced Assembly Into Surface Functionalized Multidimensional Heterostructures with Enhanced Catalytic Activity.

The self-assembly of inorganic nanocrystals offers an efficient way for the fabrication of functional materials. However, it is still challenging for the construction of multidimensional nanostructures with controllable shapes, compositions and functions. Here, a series of heterostructures in different dimensions by surface modification of polyoxometalate (POM) clusters is developed. Three kinds of POM clusters (phosphomolybdic acid (PMA), phosphotungstic acid (PTA) and silicotungstic acid (STA) and five kinds of metal oxides (TiO2, VOx, La2O3, In2O3 and Gd2O3) can be used as building blocks, and a class of 1D, 2D and 3D heterostructures can be achieved by the control of surface ligand coverage. Compared with individual building blocks and other cluster-based superstructures, TiO2-PMA superstructures exhibit enhanced catalytic activity toward thioether oxidations, which is attributed to the electron transfer between TiO2 and POM clusters.

High-entropy-perovskite subnanowires for photoelectrocatalytic coupling of methane to acetic acid.

The incorporation of multiple immiscible metals in high-entropy oxides can create the unconventional coordination environment of catalytic active sites, while the high formation temperature of high-entropy oxides results in bulk materials with low specific surface areas. Here we develop the high-entropy LaMnO3-type perovskite-polyoxometalate subnanowire heterostructures with periodically aligned high-entropy LaMnO3 oxides and polyoxometalate under a significantly reduced temperature of 100 oC, which is much lower than the temperature required by state-of-the-art calcination methods for synthesizing high-entropy oxides. The high-entropy LaMnO3-polyoxometalate subnanowires exhibit excellent catalytic activity for the photoelectrochemical coupling of methane into acetic acid under mild conditions (1 bar, 25 oC), with a high productivity (up to 4.45 mmol g‒1cat h‒1) and selectivity ( > 99%). Due to the electron delocalization at the subnanometer scale, the contiguous active sites of high-entropy LaMnO3 and polyoxometalate in the heterostructure can efficiently activate C - H bonds and stabilize the resulted *COOH intermediates, which benefits the in situ coupling of *CH3 and *COOH into acetic acid.

Homogeneous Integration of Polyoxometalates and Titania into Crumpled Layers.

The crumpling and buckling in nanosheets are anticipated to provide new characteristics that could not be observed in ideal flat layers. However, the rigid lattice structure of inorganic metal oxides limits their assembly into well-defined crumpled layers. Here, this study demonstrates that at the sub-nm scale, polyoxometalates (POMs) clusters having well-defined structures can intercede during the nucleation process of titania and co-assemble with nuclei to form uniform, large-sized crumpled binary 2D layers with a thickness of 2 nm. The obtained crumpled layers are then used as a support material to immobilize Pd nanoclusters with an average size of 2 nm. Pd-immobilized crumpled layers are employed as heterogeneous catalysts for the partial hydrogenation of acetylene. This structurally and compositionally unique heterogeneous catalyst manifests exceptional selectivity to cis-alkene with almost 100% yield as compared to commercially available titania which only exhibits 10% diphenylacetylene conversion and 42% selectivity in the given period of time.

Microwave-assisted synthesis of polyoxometalate-Dy2O3 monolayer nanosheets and nanotubes.

Two-dimensional (2D) materials have shown unique chemical and physical properties; however, their synthesis is highly dependent on the layered structure of building blocks. Herein, we developed monolayer Dy2O3-phosphomolybdic acid (PMA) nanosheets and nanotubes based on microwave synthesis. Microwave-assisted synthesis with high-energy input gives a faster and dynamically driven growth of nanomaterials, resulting in high-purity nanostructures with a narrow size distribution. The reaction times of the nanosheets and nanotubes under microwave synthesis are significantly reduced compared with oven-synthesis. Dy2O3-PMA nanosheets and nanotubes exhibit enhanced activity and stability in photoconductance, with higher sensitivities (0.308 µA cm-2 for nanosheets and 0.271 µA cm-2 for nanotubes) compared to the individual PMA (0.12 µA cm-2) and Dy2O3 (0.025 µA cm-2) building blocks. This work demonstrates the promising application potential of microwave-synthesized 2D heterostructures in superconductors and photoelectronic devices.

Fabricating sub-nanometer materials through cluster assembly.

The self-assembly of clusters provides a feasible approach for the bottom-up fabrication of functional materials with tailored properties. Sub-nanometer cluster assembly with a well-defined construction presents a precisely controllable structure and extraordinary properties, which provides an ideal model for the investigation of structures and properties at the molecular level. Non-covalent interactions between clusters may dominate the assembly behavior, appearing as tunable structures different from their nano-counterparts. Interactions between clusters and their superatom orbitals can significantly influence the electronic structures, because of which exceptional properties may emerge. In this paper, recent progress on cluster-based assemblies is introduced, including sub-nanometer building blocks of noble metal and polyoxometalate (POM) clusters. The structures, formation mechanism and properties of these cluster assemblies are discussed from experimental and theoretical aspects. This perspective aims to provide a new insight into the design and manufacture of sub-nanometer materials based on clusters.

Visible Light Induced Ag-Polyoxometalate Coassembly into Single-Cluster Nanowires.

1D superlattices with long-ranged periodicity present extraordinary application properties due to their unique electronic structures. Here, the visible light driven synthesis of 1D single-cluster chains constructed by polyoxometalate (POM) and Ag clusters is reported, where two types of clusters align alternatively along the nanowire. Low symmetrical POM clusters of [P2 W17 O61 ]10- , [P2 W15 O56 ]12- , and [EuW10 O36 ]9- can be used as building blocks. The directly bonding cluster units result in interactive electronic structures of Ag and POM clusters, as well as the greatly promoted electron transfer during the redox reaction. The Ag-P2 W17 nanowires perform significantly enhanced activities in both electrochemical sensing and catalytic gasoline desulfurization compared with individual building blocks, demonstrating the extraordinary application properties and promising potentials of cluster-based heteroconstructions.

Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores.

Two-dimensional (2D) structures have been shown to possess interesting and potentially useful properties. Because of their isotropic structure, however, clusters tend to assemble into 3D architectures. Here we report the assembly of polyoxometalate clusters into layered structures that feature uniform hexagonal pores and in-plane electron delocalization properties. Because these structures are 2D and visually reminiscent of graphene, they are referred to as 'clusterphenes'. A series of multilayer and monolayer clusterphenes have been constructed with 13 types of polyoxometalate cluster. The resulting clusterphenes were shown to exhibit substantially improved stability and catalytic efficiency towards olefin epoxidation reactions, with a turnover frequency of 4.16 h-1, which is 76.5 times that of the unassembled clusters. The catalytic activity of the clusterphenes derives from the electron delocalization between identical clusters within the 2D layer, which efficiently reduces the activation energy of the catalytic reaction.

2-Methylimidazole assisted ultrafast synthesis of carboxylate-based metal-organic framework nano-structures in aqueous medium at room temperature.

Carboxylate-based metal-organic frameworks (CMOFs) have received considerable attentions for their high stability, catalytic activity, and porosity. However, synthesis of CMOFs requires high temperature, pressure, and long reaction time. Here, we explored the activity of 2-methylimidazole (2-MIM) for ultrafast synthesis of CMOF nanostructures (CMOFNs), in aqueous medium at room temperature and reaction time of 10 min. Seven CMOFNs have been synthesized by using Al3+, Cr3+, Cu2+, Fe3+, In3+, or Cd2+ salt and 1,4-bezenedicarboxylic acid, or 1,3,5-benzenetricarboxylic acid. Through this technique, the CMOFs with space time yield 181-501 kg m-3 day-1 and crystal sizes of ca. 200-700 nm was obtained.

Single molecule-mediated assembly of polyoxometalate single-cluster rings and their three-dimensional superstructures.

The assembly of atomically precise clusters into superstructures has tremendous potential in structural tunability and applications. Here, we report a series of single-cluster nanowires, single-cluster nanorings, and three-dimensional superstructure assemblies built by POM clusters. By stepwise tuning of interactions at molecular levels, the configurations can be varied from single-cluster nanowires to nanorings. A series of single-cluster nanostructures in different configurations can be achieved with up to 15 kinds of POM clusters. The single-cluster nanowires and three-dimensional superstructures perform enhanced activity in the catalytic and electrochemical sensing fields, illustrating the universal functionality of single-cluster assemblies.