Carbon Monoxide Promotes the Catalytic Hydrogenation on Metal Cluster Catalysts.

Size effect plays a crucial role in catalytic hydrogenation. The highly dispersed ultrasmall clusters with a limited number of metal atoms are one candidate of the next generation catalysts that bridge the single-atom metal catalysts and metal nanoparticles. However, for the unfavorable electronic property and their interaction with the substrates, they usually exhibit sluggish activity. Taking advantage of the small size, their catalytic property would be mediated by surface binding species. The combination of metal cluster coordination chemistry brings new opportunity. CO poisoning is notorious for Pt group metal catalysts as the strong adsorption of CO would block the active centers. In this work, we will demonstrate that CO could serve as a promoter for the catalytic hydrogenation when ultrasmall Pd clusters are employed. By means of DFT calculations, we show that Pd n (n = 2-147) clusters display sluggish activity for hydrogenation due to the too strong binding of hydrogen atom and reaction intermediates thereon, whereas introducing CO would reduce the binding energies of vicinal sites, thus enhancing the hydrogenation reaction. Experimentally, supported Pd2CO catalysts are fabricated by depositing preestablished [Pd2(µ-CO)2Cl4]2- clusters on oxides and demonstrated as an outstanding catalyst for the hydrogenation of styrene. The promoting effect of CO is further verified experimentally by removing and reintroducing a proper amount of CO on the Pd cluster catalysts.

pH-sensitive radiolabeled and superfluorinated ultra-small palladium nanosheet as a high-performance multimodal platform for tumor theranostics.

Radiolabeled nanomaterials, especially those with ultra-small structures, have been the research focus in recent years, and thus may open up new prospects for clinical diseases theranostics. Herein, fluorinated Pd nanosheets labeled with Gd or radionuclides are developed as multimodal platforms for tumor theranostics. These nanomaterials decorated by functional polyethylene glycol demonstrate ultrahigh 19F MRI signal, ultrasmall size and good dispersibility. These ultrasmall materials exhibit good biocompatibility and easily to be modified for multimodal imaging (SPECT/MRI/PAI) by assembling the functional groups like building blocks. Furthermore, with high accumulation in tumor sites, under the guidance of multimodal imaging, combined photothermal therapy and radiotherapy are performed and synergistic effects are obtained. By comparing the in vivo behaviors of nanostructures labeled by different nuclides, the present study suggests the pH-sensitive radioiodinated Pd nanosheet which has unexpected T/NT ratio (>4-fold tumor-to-muscle ratio) in SPECT imaging and solves the critical high background issue of nanoprobes, could improve diagnostic accuracy and guide combination therapy. In summary, this functionalized nanoplatform with promising imaging and therapeutic efficacy has great potential for precision theranostic nanomedicines.

Economizing Production of Diverse 2D Layered Metal Hydroxides for Efficient Overall Water Splitting.

2D layered metal hydroxides (LMH) are promising materials for electrochemical energy conversion and storage. Compared with exfoliation of bulk layered materials, wet chemistry synthesis of 2D LMH materials under mild conditions still remains a big challenge. Here, an "MgO-mediated strategy" for mass production of various 2D LMH nanosheets is presented by hydrolyzing MgO in metal salt aqueous solutions at room temperature. Benefiting from this economical and scalable strategy, ultrathin LMH nanosheets (M = Ni, Fe, Co, NiFe, and NiCo) and their derivatives (e.g., metal oxides and sulfides) can be synthesized in high yields. More importantly, this strategy opens up opportunities to fabricate hierarchically structured LMH nanosheets, resulting in high-performance electrocatalysts for the oxygen- and hydrogen-evolution reactions to realize stable overall water splitting with a low cell voltage of 1.55 V at 10 mA cm-2 . This work provides a powerful platform for the synthesis and applications of 2D materials.

Self-supporting sulfur cathodes enabled by two-dimensional carbon yolk-shell nanosheets for high-energy-density lithium-sulfur batteries.

How to exert the energy density advantage is a key link in the development of lithium-sulfur batteries. Therefore, the performance degradation of high-sulfur-loading cathodes becomes an urgent problem to be solved at present. In addition, the volumetric capacities of high-sulfur-loading cathodes are still at a low level compared with their areal capacities. Aiming at these issues, two-dimensional carbon yolk-shell nanosheet is developed herein to construct a novel self-supporting sulfur cathode. The cathode with high-sulfur loading of 5 mg cm-2 and sulfur content of 73 wt% not only delivers an excellent rate performance and cycling stability, but also provides a favorable balance between the areal (5.7 mAh cm-2) and volumetric (1330 mAh cm-3) capacities. Remarkably, an areal capacity of 11.4 mAh cm-2 can be further achieved by increasing the sulfur loading from 5 to 10 mg cm-2. This work provides a promising direction for high-energy-density lithium-sulfur batteries.One of the challenges facing lithium-sulfur batteries is to develop cathodes with high mass and high volume loading. Here the authors show that two-dimensional carbon yolk-shell nanosheets are promising sulfur host materials, enabling stable battery cells with high energy density.

Ultrastable atomic copper nanosheets for selective electrochemical reduction of carbon dioxide.

The electrochemical conversion of CO2 and H2O into syngas using renewably generated electricity is an attractive approach to simultaneously achieve chemical fixation of CO2 and storage of renewable energy. Developing cost-effective catalysts for selective electroreduction of CO2 into CO is essential to the practical applications of the approach. We report a simple synthetic strategy for the preparation of ultrathin Cu/Ni(OH)2 nanosheets as an excellent cost-effective catalyst for the electrochemical conversion of CO2 and H2O into tunable syngas under low overpotentials. These hybrid nanosheets with Cu(0)-enriched surface behave like noble metal nanocatalysts in both air stability and catalysis. Uniquely, Cu(0) within the nanosheets is stable against air oxidation for months because of the presence of formate on their surface. With the presence of atomically thick ultrastable Cu nanosheets, the hybrid Cu/Ni(OH)2 nanosheets display both excellent activity and selectivity in the electroreduction of CO2 to CO. At a low overpotential of 0.39 V, the nanosheets provide a current density of 4.3 mA/cm2 with a CO faradaic efficiency of 92%. No decay in the current is observed for more than 22 hours. The catalysts developed in this work are promising for building low-cost CO2 electrolyzers to produce CO.

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst.

Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni-Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources.

Photochemical route for synthesizing atomically dispersed palladium catalysts.

Atomically dispersed noble metal catalysts often exhibit high catalytic performances, but the metal loading density must be kept low (usually below 0.5%) to avoid the formation of metal nanoparticles through sintering. We report a photochemical strategy to fabricate a stable atomically dispersed palladium-titanium oxide catalyst (Pd1/TiO2) on ethylene glycolate (EG)-stabilized ultrathin TiO2 nanosheets containing Pd up to 1.5%. The Pd1/TiO2 catalyst exhibited high catalytic activity in hydrogenation of C=C bonds, exceeding that of surface Pd atoms on commercial Pd catalysts by a factor of 9. No decay in the activity was observed for 20 cycles. More important, the Pd1/TiO2-EG system could activate H2 in a heterolytic pathway, leading to a catalytic enhancement in hydrogenation of aldehydes by a factor of more than 55.

Carbon Monoxide-Assisted Synthesis of Ultrathin PtCu3 Alloy Wavy Nanowires and Their Enhanced Electrocatalysis.

Glucose sensing that is not influenced by the presence of chloride, uric acid, ascorbic acid and dopamine is achieved on ultrathin PtCu3 alloy wavy nanowires (WNWs). These WNWs are synthesized by a facile, one-pot, templateless hydrothermal method in an atmosphere of CO, which is critical to the formation process. Their structural properties, including the abundance of twinning defects, make the as-prepared PtCu3 WNWs excellent electrocatalysts for methanol oxidation as well as great sensors for glucose.

Trace surface-clean palladium nanosheets as a conductivity enhancer in hole-transporting layers to improve the overall performances of perovskite solar cells.

Surface-clean Pd nanosheets were synthesized and embedded in a hole transport material (HTM) matrix to improve the conductivity of the HTM layer. Applying only a trace amount of Pd nanosheets readily led to a remarkably enhanced performance of perovskite solar cells (PSCs). This finding provides an effective strategy to build efficient charge-transport materials for improving the overall performance of PSCs.

An investigation of the mimetic enzyme activity of two-dimensional Pd-based nanostructures.

In this work, we investigated the mimetic enzyme activity of two-dimensional (2D) Pd-based nanostructures (e.g. Pd nanosheets, Pd@Au and Pd@Pt nanoplates) and found that they possess intrinsic peroxidase-, oxidase- and catalase-like activities. These nanostructures were able to activate hydrogen peroxide or dissolved oxygen for catalyzing the oxidation of organic substrates, and decompose hydrogen peroxide to generate oxygen. More systematic investigations revealed that the peroxidase-like activities of these Pd-based nanomaterials were highly structure- and composition-dependent. Among them, Pd@Pt nanoplates displayed the highest peroxidase-like activity. Based on these findings, Pd-based nanostructures were applied for the colorimetric detection of H2O2 and glucose, and also the electro-catalytic reduction of H2O2. This work offers a promising prospect for the application of 2D noble metal nanostructures in biocatalysis.

Two-dimensional antibacterial Pd@Ag nanosheets with a synergetic effect of plasmonic heating and Ag+ release.

In this work, a novel bactericidal agent based on two-dimensional Pd@Ag nanosheets (Pd@Ag NSs) that is responsive to near-infrared (NIR) light has been developed. These Pd@Ag NSs were prepared by reducing silver ions on the surface of Pd nanosheets (Pd NSs) seeds by formaldehyde, and displayed excellent NIR absorption and photothermal conversion properties. In addition, the NIR irradiation triggers the release of more Ag+ from the Pd@Ag NSs. Upon exposure to a NIR laser at a low power density (0.5 W cm-2), Pd@Ag NSs kill both Gram-negative (Escherichia coli, E. coli) and Gram-positive (Staphylococcus aureus, S. aureus) bacteria effectively by the synergistic effect of plasmonic heating and Ag+ release, which is much higher than either plasmonic heating or Ag+ alone. Such a novel nanomaterial is promising as an adjuvant therapeutic method for the treatment of patients suffering from severe bacterial infections.

Core-shell Pd@Au nanoplates as theranostic agents for in-vivo photoacoustic imaging, CT imaging, and photothermal therapy.

Uniform plasmonic Pd@Au core-shell bimetallic nanoplates are synthesized by seeded growth strategy. Surface modified with SH-PEG makes it good biocompatibility, prolonged blood circulation, and relatively high tumor accumulation. Enhanced tumor contrast effects can be obtained for in vivo photoacoustic/CT imaging after intravenous injection of Pd@Au-PEG. Moreover, efficient photothermal tumor ablation is achieved, guided by the imaging techniques. This work promises further exploration of the superiority of 2D nanostructures for in vivo biomedical applications.