Metal Oxide Clusters Research Articles

Cubic-like A4B4 (A = Be, Mg, Ca; B = O) clusters for novel potential applications under density functional study

A density functional investigation of A4B4 (A = Be, Mg, Ca; B = O) metal-oxide clusters series is carried out in search for the stable and potential candidates. The minimum energy isomers for each of the A4B4 systems are identified, and frontier molecular orbitals (FMOs) have been generated and analyzed for the same. It is noteworthy that two nearly cubic-like stable motifs have been identified along with favorable electronic and optical properties that may be utilized for developing novel, useful nanomaterials. All the A4O4 systems revealed to be of cubic-like lowest energy structures, very interestingly, cubic Mg4O4 (λ = 418 Å) and cubic Ca4O4 (λ = 552 Å) are obtained as visible active clusters, which certainly confirms their promises in developing novel cluster-assembled nanomaterials with different dimensions with applications in optical and semiconductor arenas. Simulated infrared spectra of these identified novel cubic-like cluster-building units might help experimentalists with the possible synthesis and applications.

Reactivity of Atomic Oxygen Radical Anions in Metal Oxide Clusters.

Atomic oxygen radical anion (O⋅-) represents an important type of reactive centre that exists in both chemical and biological systems. Gas-phase atomic clusters can be studied under isolated and well controlled conditions. Studies of O⋅--containing clusters in the gas-phase provide a unique strategy to interpret the chemistry of O⋅- radicals at a strictly molecular level. This review summarizes the research progresses made since 2013 for the reactivity of O⋅- radicals in the atomically precise metal oxide clusters including negatively charged, nanosized, and neutral heteronuclear metal clusters benefitting from the development of advanced experimental techniques. New electronic and geometric factors to control the reactivity and product selectivity of O⋅- radicals under dark and photo-irradiation conditions have been revealed. The detailed mechanisms of O⋅- generation have been discussed for the reaction systems of nanosized and heteroatom-doped metal oxide clusters. The catalytic reactions mediated by the O⋅- radicals in metal clusters have also been successfully established and the microscopic mechanisms about the dynamic generation and depletion of O⋅- radicals have been clearly understood. The studies of O⋅- containing metal oxide clusters in the gas-phase provided new insights into the chemistry of reactive oxygen species in related condensed-phase systems.

On the Nature of HOPG-Supported Pt1Ti2O7 and its Decomposition of a Nerve Agent Simulant: A Cluster Model of a Single Atom Catalyst Active Site.

Chemical weapons, including hyper lethal nerve agents, are a persistently looming threat across the modern geopolitical landscape. There is a pressing need for the design and development of improved protective materials, which can be substantially aided by the cultivation of a fundamental molecular-level understanding of candidate systems and the corresponding decomposition chemistry. The emergence of the exciting new class of single atom catalyst (SAC) materials has enhanced the prospect of subnanoscale design tailoring in the hopes of optimizing activity and selectivity for a variety of chemical applications. Here, we apply our recently developed experimental technique for modeling the active sites of such SAC materials through the preparation of surface supported size-selected single metal-atom doped metal oxide clusters. The propensity for an SAC cluster model system for Pt1/TiO2 materials, Pt1Ti2O7 supported on highly oriented pyrolytic graphite (HOPG), to adsorb and decompose nerve agent simulant dimethyl methylphosphonate (DMMP) was investigated through a combination of temperature-programmed desorption/reaction (TPD/R) and X-ray photoelectron spectroscopy (XPS). XPS measurements of the as-prepared Pt1Ti2O7 clusters supported the successful isolation of single Pt atoms in clusters monodispersed across the HOPG surface. TPD/R experiments showed that the reactivity exhibited by the Pt1Ti2O7 clusters was distinct from that of Ti2O7 clusters lacking the single Pt atom. It was found that DMMP decomposed over Pt1Ti2O7 upon heating to as low as room temperature, and higher temperature treatments evolved exclusively H2O, CO, and H2, while decomposition over Ti2O7 evolved only methanol and formaldehyde at elevated temperatures. This indicated the promotion of C-H and PO-C bond cleavage within DMMP due to the presence of single Pt atoms in the clusters. Further, the Pt1Ti2O7 clusters were found to desorb P-containing decomposition species, preventing active site poisoning; however, a change of reactivity reflecting that of Ti2O7 was observed following a single TPD/R cycle. This suggested the encapsulation of active Pt sites by titanium oxide during high temperature treatment and is thus an issue deserving of serious attention in the study of Pt1/Ti2O7 SAC materials.

Mass spectrometry provides insights into the structures of polyoxovanadate alkoxide clusters substituted with Fe and W heterometals

Atom-by-atom substitution is a promising strategy for tailoring the electronic properties of transition metal oxide clusters. This approach typically generates a mixture of species that are difficult to separate using conventional methods. As a result, the characterization of their structures and electronic properties remains challenging. Herein, we use collision-induced dissociation (CID) to study the fragmentation of well-defined Fe- and W-doped Lindquist polyoxovanadate methoxides synthesized as a mixture of singly and doubly substituted species. Fragmentation reveals that Fe heteroatoms are efficiently retained within the metal oxide core. In contrast, one W atom is incorporated into the primary WO2(OCH3)2 neutral loss from both the singly and doubly substituted W-containing clusters. Collision energy-resolved CID provides insights into the fragmentation pathways, which are compared to those of the homometallic polyoxovanadate methoxide species. The incorporation of Fe into the cluster reduces its stability towards fragmentation, which could be attributed to the increase in the relative stability of Fe-containing fragment ions with four metal atoms in comparison with their homometallic analog. The observed fragmentation is rationalized by assuming that Fe atoms are incorporated within the low valent plane, while one W atom occupies the axial out-of-plane position in the cluster.

Construction of ROS-balancing-engineered heterojunction photoswitch for achieving programmed inflammatory management and tissue regeneration

Early instigation and subsequent attenuation of inflammation are crucial for tissue regeneration, which poses a need for inflammatory regulation in the design of materials. In this work, a novel photocatalytic heterojunction consist of MXene, Zr-based porphyrinic metal–organic framework (named PCN-222), and Pt nanoparticles (termed MX/PCN@Pt HJs) is developed to achieve photo-controlled reactive oxygen species (ROS) generation and clearance. According to density function theory calculations and related experiments, the unique heterojunction formed by MXene and MOFs, abundant O2 adsorption sites of metal oxide clusters, and porous features of MOFs promoted the adsorption of active reactants and accelerated electron transfer, thereby exhibiting excellent photocatalytic performance. Meanwhile, the PCN-222 with superoxide dismutase (SOD) activity and Pt nanoparticles with catalase (CAT) activity endowed the MX/PCN@Pt HJs with SOD/CAT mimetic cascade performance. Through the photo-controlled regulation, the MX/PCN@Pt HJs acted as a photoswitch that flexibly achieved the switch between ROS generation and clearance. Effective production of ROS not only enabled antimicrobial activity but also contributed to a pro-inflammatory state; while the timely ROS scavenging activity effectively prevented the detrimental effects of sustained inflammation. Both in vitro and in vivo evaluations had confirmed the inflammatory modulation and tissue regeneration potency of the MX/PCN@Pt HJs based on the ROS-regulated strategy, which offer a vital understanding of the MOF-based photocatalytic heterojunction for programmed inflammatory regulation.

Chemistry of Formate and Water Ligands on Metal Oxide Cluster Nodes of Metal-Organic Framework hcp Hf-UiO-66: Keys to Understanding Reactivity of Paired μ2-OH and Defect Sites.

Many metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters, and ligands that have been observed on these nodes include formates, acetates, water, hydroxyl groups, and others, all of which are potentially important in affecting reactivities for applications in separations, catalysis, and sensing. Formate is a common node ligand, arising from formic acid used as a modulator and from N,N-dimethylformamide used as a solvent in MOF syntheses. Yet only little work has been reported characterizing the reactivities of node formate ligands. Infrared spectra reported here show that formate bonds to two types of sites on the paired Hf6O8 nodes of hcp UiO-66, namely, defect and μ2-OH sites. Quantifying the number of formate ligands by 1H NMR spectroscopy of digested samples showed an almost equal number of formate ligands on the two sites, indicating the likelihood that they neighbor each other. These formate ligands interact with water molecules, reversibly switching their bonding from bidentate to monodentate. The formates on μ2-OH sites of hcp Hf-UiO-66 interact much more strongly with water than those on defect sites of the same node, and both interact more strongly than isolated defect sites of Hf-UiO-66. Correspondingly, the catalytic activities of hcp UiO-66 determined as turnover frequencies on each site are approximately twofold higher than those on UiO-66, bolstering the inference that methanol dehydration is catalyzed by a node defect site and a neighboring node μ2-OH site. The results show how MOFs, with their well-defined node structures, provide unprecedented opportunities to understand details of reactivities and catalysis on metal oxide clusters, in contrast to bulk metal oxide surfaces.

The Hybridization of Polymers with Metal Oxide Clusters for the Design of Non-Fluorinated Proton Exchange Membranes.

As the key component of various energy storage and conversion devices, proton exchange membranes (PEMs) have been attracting significant interest. However, their further development is limited by the high cost of perfluorosulfonic acid polymers and the poor stability of acid-dopped non-fluorinated polymers. Recently, a new group of PEMs has been developed by hybridizing polyoxometalates (POMs), a group of super acidic sub-nanoscale metal oxide clusters, with polymers. POMs can serve simultaneously as both proton sponges and stabilizing agents, and their complexation with polymers can further improve polymers' mechanical performance and processability. Enormous efforts have been focused on studying supramolecular complexation or covalent grafting of POMs with various polymers to optimize PEMs in terms of cost, mechanical properties and stabilities. This concept summarizes recent advances in this emerging field and outlines the design strategies and application perspectives employed for using POM-polymer hybrid materials as PEMs.

Experimental Reactivity of (MoO3)NO- (N = 1-21) Cluster Anions with C1-C4 Alkanes: A Simple Model to Predict the Reactivity with Methane.

Metal oxide clusters with atomic oxygen radical anions are important model systems to study the mechanisms of activating and transforming very stable alkane molecules under ambient conditions. It is extremely challenging to characterize the activation and conversion of methane, the most stable alkane molecule, by metal oxide cluster anions due to the low reactivity of the anionic species. In this study, using a ship-lock type reactor that could be run at relatively high pressure conditions to provide a high number of collisions in ion-molecule reactions, the rate constants of the reactions between (MoO3)NO- (N = 1-21) cluster anions and the light alkanes (C1-C4) were measured under thermal collision conditions. The relationships among the reaction rates of different alkanes were obtained to establish a model to predict the low rate constants with methane from the high rate constants with C2-C4 alkanes. The model was tested by using available experimental results in literature. This study provides a new method to estimate the relatively low reactivity of atomic oxygen radical anions with methane on metal oxide clusters.

Vapor Phase Infiltration of Titanium Oxide into P3HT to Create Organic-Inorganic Hybrid Photocatalysts.

Herein, we report for the first time the use of vapor phase infiltration (VPI) to infuse conducting polymers with inorganic metal oxide clusters that together form a photocatalytic material. While vapor infiltration has previously been used to electrically dope conjugated polymers, this is the first time, to our knowledge, that the resultant hybrid material has been demonstrated to have photocatalytic properties. The system studied is poly(3-hexylthiophene-2,5-diyl) (P3HT) vapor infiltrated with TiCl4 and H2O to create P3HT-TiOx organic-inorganic hybrid photocatalytic materials. X-ray photoelectron spectroscopy analysis shows that P3HT-TiOx VPI films consist of a partially oxidized P3HT matrix, and the infiltrated titanium inorganic is in a 4+ oxidation state with mostly oxide coordination. Upon visible light illumination, these P3HT-TiOx hybrids degrade methylene blue dye molecules. The P3HT-TiOx hybrids are 4.6× more photocatalytically active than either the P3HT or TiO2 individually or when sequentially deposited (e.g., P3HT on TiO2). On a per surface area basis, these hybrid photocatalysts are comparable or better than other best in class polymer semiconductor photocatalysts. VPI of TiCl4 + H2O into P3HT makes a unique hybrid structure and idealized photocatalyst architecture by creating nanoscale TiOx clusters concentrated toward the surface achieving extremely high catalytic rates. The mechanism for this enhanced photocatalytic rate is understood using photoluminescence spectroscopy, which shows significant quenching of excitons in P3HT-TiOx as compared to neat P3HT, indicating that P3HT acts as a photosensitizer for the TiOx catalyst sites in the hybrid material. This work introduces a new approach to designing and synthesizing organic-inorganic hybrid photocatalytic materials, with expansive opportunities for further exploration and optimization.

Polyoxometalate/MOF-derived MoSe2/(Ni, Co)Se2 for battery-type electrodes of high-performance supercapacitors

Polyoxometalates (POMs), as multinuclear metal oxide clusters, possess natural multi-electron redox properties and high electrical conductivity. However, their susceptibility to leaching and agglomeration limits their application in energy storage. MOF materials provide a solution to the limitation of POMs due to their controllable pore sizes, big surface areas and strong adsorption properties. The synergistic effect between the two components greatly improves the electrochemical properties of the composites. In view of this, PMo12 is encapsulated in ZIF-67 to form PMo12@ZIF-67 by in situ self-assembly, and benefitted from this unique precursor, MoSe2/(Ni, Co)Se2 hollow structures assembled by nanoparticles are synthesized though Ni2+ etching and selenization process. At the same time, the PMo12 content is optimized to get the best performance of 60-MoSe2/(Ni, Co)Se2. In the three-electrode test, the developed 60-MoSe2/(Ni, Co)Se2 electrode material exhibits an excellent specific capacity of 359.9 mA h g−1 at a current density of 1 A g−1, and a capacitance retention rate of 83.7 % after 10,000 cycles. In addition, the asymmetric supercapacitor (ASC) assembled with a positive electrode of 60-MoSe2/(Ni, Co)Se2 and a negative electrode of activated carbon exhibits an excellent energy density of 40.3 W h kg−1 at a power density of 800.9 W kg−1. These superior electrochemical properties are attributed to the unique electronic structure of PMo12, which further demonstrates the feasibility of constructing hollow multicomponent selenides as energy storage materials using PMo12-ZIF-67 as a precursor.

Polyoxometalate functionalized magnetic metal-organic framework with multi-affinity sites for efficient enrichment of phosphopeptides.

The reasonable design of metal-organic framework (MOF)-derived nanomaterial has important meaning in increasing the enrichment efficiency in the study of protein phosphorylation. In this work, a polyoxometalate (POM) functionalized magnetic MOF nanomaterial (Fe3O4@MIL-125-POM) was designed and fabricated. The nanomaterial with multi-affinity sites (unsaturated metal sites and metal oxide clusters) was used for the enrichment of phosphopeptides. Fe3O4@MIL-125-POM had high-efficient enrichment performance towards phosphopeptides (selectivity, a mass ratio of bovine serum albumin/α-casein/β-casein at 5000:1:1; sensitivity, 0.1 fmol; satisfactory repeatability, ten times). Furthermore, Fe3O4@MIL-125-POM was employed to enrich phosphopeptides from non-fat milk digests, saliva, serum, and A549 cell lysate. The enrichment results illustrated the great potential of Fe3O4@MIL-125-POM for efficient identification of low-abundance phosphopeptides.

Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility.

Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti8Ce2-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti8Ce2-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

Unraveling NH3-SCR performance and the role of Fe and Cu over the supported TNU-9 catalysts

Enlarging reaction temperature and raising the resistance of SO2 and H2O for NH3-SCR is still a challenge. Meanwhile, the role of Fe and Cu over the supported TNU-9 catalysts is not so clear either for NH3-SCR reaction. Aiming at the above-mentioned problems, Fe and Cu bimetallic co-doped TNU-9 catalysts were prepared by solution ion-exchanged method and the effect of the exchanged order of Fe and Cu on NH3-SCR activity was conducted. What's more, the resistance of SO2/H2O and DFT calculations are also investigated. As a comparison, the activity Fe/T9 and Cu/T9 were examined. The reason that the different activity of Fe and Cu was also explained through DFT calculations. The glorious catalyst, Cu-2Fe/T9 synthesized via exchanging Cu first for twice and then Fe for once, demonstrated outstanding catalytic performance with the NOx conversion ca. 100 % at 225–450 °C and exceeding 80 % in the temperature range of 200–500 °C. It was attributed to minimizing the oxidation of Fe2+. And the most amazing thing was that Cu-2Fe/T9 had better the resistance of SO2 and worse the resistance of H2O than Cu/T9 at 225 °C. It was because that SO2 was more easily adsorbed at the Fe site, resulting in Fe protecting the active site Cu and the sulfation also provided more strong acidic sites, which were confirmed by DFT calculations and NH3-TPD. In addition, monomeric iron was more susceptible to water and the migration of ion-exchanged iron aggregated to form metal oxide clusters.

Precise Distance Control and Functionality Adjustment of Frustrated Lewis Pairs in Metal-Organic Frameworks.

We report the construction of frustrated Lewis pairs (FLPs) in a metal-organic framework (MOF), where both Lewis acid (LA) and Lewis base (LB) are fixed to the backbone. The anchoring of a tritopic organoboron linker as LA and a monotopic linker as LB to separate metal oxide clusters in a tetrahedron geometry allows for the precise control of distance between them. As the type of monotopic LB linker varies, pyridine, phenol, aniline, and benzyl alcohol, a series of 11 FLPs were constructed to give fixed distances of 7.1, 5.5, 5.4, and 4.8 Å, respectively, revealed by 11B-1H solid-state nuclear magnetic resonance spectroscopy. Keeping LA and LB apart by a fixed distance makes it possible to investigate the electrostatic effect by changing the functional groups in the monotopic LB linker, while the LA counterpart remains unaffected. This approach offers new chemical environments of the active site for FLP-induced catalysis.

Probing the sites on metal oxide cluster nodes of metal organic framework MIL-96, MIL-100 and MIL-110

Metal oxide cluster MOF nodes are a good platform to understand the reactivities and catalysis. MIL-96, MIL-100 and MIL-110 are drastically different in their node structures. Following our previous reported results for MIL-100, we report the modified synthesis and characterization of the node sites of MIL-110 and MIL-96 and their catalytic sites by using methanol dehydration as probe reaction. We show that these MOFs can be synthesized from the same solution by adding various amounts of formic acid as modulator. Herein, the chemistry of hydroxyl, formate and methoxy groups were used to probe the three MOFs’ node sites. IR data show the bonding structures of these ligands are highly diverse, with reactivities and flexibilities depending on node sites. We identified terminal OH group and various µ2-OH groups in single, paired or hydrogen bonded modes on the MOF nodes. Formate ligands were introduced to the node sites during the synthesis or by a post treatment in formic acid/DMF solution. Surprisingly, the bonding modes of formate ligands on Al3(OH)3 node structure of MIL-96 can be reversibly switched between monodentate and bidentate through a process induced by water molecules. Further, methoxy ligands—likely to be the intermediate for catalytic reaction—were also observed on the node sites under methanol dehydration conditions at 250 ℃. The activities of MIL-100 and MIL-96 for methanol dehydration determined by TOF per node were similar, both approximately 3-fold higher than that of MIL-110. The data suggests that catalytic sites incorporate adjacent vacancy and defect node sites, which constitute a minority among all observed MOF node sites. We foresee the opportunities in expanding the chemistry and understanding into other MOFs with metal oxide cluster nodes.

Supramolecular complexation of metal oxide clusters in PVDF-PVP blends for large scale fabrication of proton exchange membranes for fuel cells

The perfluorosulfonic acid (PFSA) polymers have achieved great success as proton exchange membranes (PEMs) in various energy storage and conversion devices; nevertheless, the improvements regarding PEMs' synthetic cost, mechanical properties, stability and processability are still urgently required. Herein, 1 nm super acidic metal oxide cluster, H3PW12O40 (PW12), is complexed with the blends of polyvinylpyrrolidone (PVP) and polyvinylidene fluoride (PVDF) to afford nanocomposite PEMs that enables the stable and effective operation of hydrogen fuel cell devices. As the polymer matrix, the PVDF is blended with PVP via inter-chain hydrogen bonding to provide mechanical support for the nanocomposite PEMs. The further introduced PW12 clusters can interact strongly with PVP via electrostatic attraction to enhance the PEMs' mechanical strength (E = 231 MPa) and prevent the leaching of PW12 for long-term stability. Meanwhile, the incorporation of the super acidic PW12 can facilitate the fast proton transportation and therefore, lead to the significant increasement of proton conductivity to 9.8 × 10−3 S cm−1 at 70 °C and 100% RH. Due to the excellent mechanical properties and the supramolecular interaction among the components, the PEMs’ thickness can be controlled to be challenging ∼10μm for feasible large-scale continuous processing. Finally, the molecular design enables the successful fabrication of the nanocomposite PEMs into fuel cell devices with the power density as 342.8 mW cm−2. The studies not only shed light on the structure-properties of polymer nanocomposites, but also pave avenues to the design of robust composite PEMs for fuel cell appliacations.

Eddavidite, Cu12Pb2O15Br2, a New Mineral Species, and Its Solid Solution with Murdochite, Cu12Pb2O15Cl2

Eddavidite is a new mineral species (IMA2018-010) with ideal formula, Cu12Pb2O15Br2, and cubic Fm3¯m symmetry: a = 9.2407(9) Å; V = 789.1(2) Å3; Z = 2. Eddavidite is the bromine analog of murdochite, Cu12Pb2O15Cl2, with which it forms a solid solution series. The type locality is the Southwest mine, Bisbee, Cochise County, Arizona, U.S.A. Eddavidite also occurs in the Ojuela mine, Mapimí, Durango, Mexico. Eddavidite occurs as domains within mixed murdochite–eddavidite crystals. The empirical formula, normalized to 12 Cu apfu, is Cu12(Pb1.92Fe0.06Si0.06)(O15.08F0.02)-(Br0.99Cl0.89☐0.12). Type locality samples contain up to 67% eddavidite component, while Ojuela mine samples contain up to 62%. Mixed eddavidite–murdochite crystals show forms {100} and {111}; the habit grades from cubic through cuboctahedral to octahedral. Mixed eddavidite–-murdochite crystals exhibit good cleavage on {111}. Eddavidite is black, opaque with submetallic luster, and visually indistinguishable from intergrown murdochite. Its Mohs hardness is 4; dmeas. = 6.33 g/cm3, dcalc. = 6.45 g/cm3. The crystal structure, refined to R = 0.0112, consists of corner-sharing square planar CuO4 units, arranged in Cu12O24 metal oxide clusters, which encapsulate Br atoms. PbO8 cubes share edges with Cu12O24 clusters in a continuous framework. Eddavidite incorporates bromine remaining after desiccation of paleo-seawater at its two known localities, which were both once situated along the Western Interior Seaway.

1 nm Tin Oxide Cluster for the Electrochemical Conversion of Carbon Dioxide to Formate at Low Overpotential

Due to its cost-effectiveness and high product selectivity, tin oxide has been regarded as a promising catalyst for the electrochemical conversion of CO2 to formate. However, formate production is hindered by the high overpotential; there is a need to reduce the overpotential to enhance energy efficiency and lower electricity cost for the implementation of carbon utilization technology. Here, we report a facile synthesis method for 1 nm-sized SnO2 cluster catalysts, which can be used for CO2-to-formate conversion. SnO2 clusters were prepared through impregnation of porous carbon with a tin precursor solution. The SnO2 clusters showed a low overpotential, generating a current density of 10 mA cm-2 at a potential of -0.34 V vs. RHE in 1 M KOH. They also achieved high Faradaic efficiencies of 90.5% and 81.5% at 200 and 300 mA cm−2, respectively. Their electrocatalytic performance was strongly dependent on the annealing conditions, which affected the particle size, electrochemical active surface area, and metal oxidation state. This paper presents a versatile method for synthesizing metal oxide cluster catalysts, apart from providing insights into the catalytic activity for the electrochemical conversion of CO2 to formate.

Thermal Reactions of NiAl3O6+ and Al4O6+ with Methane: Reactivity Enhancement by Doping.

Investigation of the reactivity of heteronuclear metal oxide clusters is an important way to uncover the molecular-level mechanisms of the doping effect. Herein, we performed a comparative study on the reactions of CH4 with NiAl3O6+ and Al4O6+ cluster cations at room temperature to understand the role of Ni during the activation and transformation of methane. Mass spectrometric experiments identify that both NiAl3O6+ and Al4O6+ could bring about hydrogen atom abstraction reaction to generate CH3• radical; however, only NiAl3O6+ has the potential to stabilize [CH3] moiety and then transform [CH3] to CH2O. Density functional theory calculations demonstrate that the terminal oxygen radicals (Ot-•) bound to Al act as the reactive sites for the two clusters to activate the first C-H bond. Although the Ni atom cannot directly participate in methane activation, it can manipulate the electronic environment of the surrounding bridging oxygen atoms (Ob) and enable such Ob to function as an electron reservoir to help Ot-• oxidize CH4 to [H-O-CH3]. The facile reduction of Ni3+ to Ni+ also facilitates the subsequent step of activating the second C-H bond by the bridging "lattice oxygen" (Ob2-), finally enabling the oxidation of methane into formaldehyde. The important role of the dopant Ni played in improving the product selectivity of CH2O for methane conversion discovered in this study allows us to have a possible molecule-level understanding of the excellent performance of the catalysts doping with nickel.

Supramolecular Complexation of Metal Oxide Cluster and Non‐Fluorinated Polymer for Large‐Scale Fabrication of Proton Exchange Membranes for High‐Power‐Density Fuel Cells

AbstractCost‐effective, non‐fluorinated polymer proton exchange membranes (PEMs) are highly desirable in emerging hydrogen fuel cells (FCs) technology; however, their low proton conductivities and poor chemical and dimension stabilities hinder their further development as alternatives to commercial Nafion®. Here, we report the inorganic‐organic hybridization strategy by facilely complexing commercial polymers, polyvinyl butyral (PVB), with inorganic molecular nanoparticles, H3PW12O40 (PW) via supramolecular interaction. The strong affinity among them endows the obtained nanocomposites amphiphilicity and further lead to phase separation for bi‐continuous structures with both inter‐connected proton transportation channels and robust polymer scaffold, enabling high proton conductivities, mechanical/dimension stability and barrier performance, and the H2/O2 FCs equipped with the composite PEM show promising power densities and long‐term stability. Interestingly, the hybrid PEM can be fabricated continuously in large scale at challenging ~10 μm thickness via typical tape casting technique originated from their facile complexing strategy and the hybrids’ excellent mechanical properties. This work not only provides potential material systems for commercial PEMs, but also raises interest for the research on hybrid composites for PEMs.