Improved Selectivity and Stability in Methane Dry Reforming by Atomic Layer Deposition on Ni-CeO2-ZrO2/Al2O3 Catalysts.

Ni can be used as a catalyst for dry reforming of methane (DRM), replacing more expensive and less abundant noble metal catalysts (Pt, Pd, and Rh) with little sacrifice in activity. Ni catalysts deactivate quickly under realistic DRM conditions. Rare earth oxides such as CeO2, or as CeO2-ZrO2-Al2O3 (CZA), are supports that improve both the activity and stability of Ni DRM systems due to their redox activity. However, redox-active supports can also enhance the undesired reverse water gas shift (RWGS) reaction, reducing the hydrogen selectivity. In this work, Ni on CZA was coated with an ultrathin Al2O3 overlayer using atomic layer deposition (ALD) to study the effects of the overlayer on catalyst activity, stability, and H2/CO ratio. A low-conversion screening method revealed improved DRM activity and lower coking rate upon the addition of the Al2O3 ALD overcoat, and improvements were subsequently confirmed in a high-conversion reactor at long times onstream. The overcoated samples gave an H2/CO ratio of ∼1 at high conversion, much greater than uncoated catalysts, and no evidence of deactivation. Characterization of used (but still active) catalysts using several techniques suggests that active Ni is in formal oxidation state >0, Ni-Ce-Al is most likely present as a mixed oxide at the surface, and a nominal thickness of 0.5 nm for the Al2O3 overcoat is optimal.

Solvent-Free Depolymerization of Plastic Waste Enabled by Plastic-Catalyst Interfacial Engineering.

Depolymerization of condensation polymers by chemolysis often suffers from the large usage of solvents and homogeneous catalysts such as acids, bases, and metal salts. The catalytic efficiency of heterogeneous catalysts is largely constrained by the poor interfacial contact between solid catalysts and solid plastics below melting points. We report here our discovery of autogenous heterogeneous catalyst layer on polyethylene terephthalate surfaces during the generally believed homogeneous catalytic depolymerization process. Inspired by the "contact mass" concept in industrial chlorosilane production, we further demonstrate that the construction of plastic-catalyst solid-solid interfaces enables solvent-free depolymerization of polyethylene terephthalate by vapor phase methanolysis at relatively low temperatures. Trace amounts of earth-abundant element (zinc) introduced by electrostatic adsorption is sufficient for catalyzing the depolymerization. The concept of plastic-catalyst contact mass interfacial catalysis might inspire new pathways for tackling plastic waste problems.

Elucidating the Roles of Amorphous Alumina Overcoat in Palladium-Catalyzed Selective Hydrogenation.

Amorphous alumina overcoats generated by atomic layer deposition (ALD) have been shown to improve the selectivity and durability of supported metal catalysts in many reactions. Several mechanisms have been proposed to explain the enhanced catalytic performance, but the accessibilities of reactants through the amorphous overcoats remain elusive, which is crucial for understanding reaction mechanisms. Here, we show that an AlOx ALD overcoat is able to improve the alkene product selectivity of a supported Pd catalyst in acetylene (C2H2) hydrogenation. We further demonstrate that the AlOx ALD overcoat blocks the access of C2H2 (kinetic diameter of 0.33 nm), O2 (0.35 nm), and CO (0.38 nm) but allows H2 (0.29 nm) to access Pd surfaces. A H-D exchange experiment suggests that H2 might dissociate heterolytically at the Pd-AlOx interface. These findings are in favor of a hydrogen spillover mechanism.

Elucidating the surface compositions of Pd@PtnL core-shell nanocrystals through catalytic reactions and spectroscopy probes.

The catalytic behaviors or properties of bimetallic catalysts are highly dependent on the surface composition, but it has been a grand challenge to acquire such information. In this work, we employ Pd@PtnL core-shell nanocrystals with an octahedral shape and tunable Pt shell thickness as a model system to elucidate their surface compositions using catalytic reactions based upon the selective hydrogenation of butadiene and acetylene. Our results indicate that the surface of the core-shell nanocrystals changed from Pt-rich to Pd-rich when they were subjected to calcination under oxygen, a critical step involved in the preparation of many industrial catalysts. The inside-out migration can be attributed to both atomic interdiffusion and the oxidation of Pd atoms during the calcination process. The changes in surface composition were further confirmed using infrared and X-ray photoelectron spectroscopy. This work offers insightful guidance for the development and optimization of bimetallic catalysts toward various reactions.

Construction of Inverse Metal-Zeolite Interfaces via Area-Selective Atomic Layer Deposition.

The spatial confinement at metal-zeolite interfaces offers a powerful knob to steer the selectivity of chemical reactions on metal catalysts. However, encapsulating metal catalysts into small-pore zeolites remains a challenging task. Here, we demonstrate an inverse design of metal-zeolite interfaces, "metal-on-zeolite," constructed by area-selective atomic layer deposition. This inverse design bypasses the intrinsic synthetic issues associated with metal encapsulation, offering a potential solution for the fabrication of task-specific metal-zeolite interfaces for desired catalytic applications. Infrared spectroscopy and several probe reactions confirmed the spatial confinement effects at the inverse metal-zeolite interfaces.

Critical Coupling of Visible Light Extends Hot-Electron Lifetimes for H2O2 Synthesis.

Devices driven by above-equilibrium "hot" electrons are appealing for photocatalytic technologies, such as in situ H2O2 synthesis, but currently suffer from low (<1%) overall quantum efficiencies. Gold nanostructures excited by visible light generate hot electrons that can inject into a neighboring semiconductor to drive electrochemical reactions. Here, we designed and studied a metal-insulator-metal (MIM) structure of Au nanoparticles on a ZnO/TiO2/Al film stack, deposited through room-temperature, lithography-free methods. Light absorption, electron injection efficiency, and photocatalytic yield in this device are superior in comparison to the same stack without Al. Our device absorbs >60% of light at the Au localized surface plasmon resonance (LSPR) peak near 530 nm-a 5-fold enhancement in Au absorption due to critical coupling to an Al film. Furthermore, we show through ultrafast pump-probe spectroscopy that the Al-coupled samples exhibit a nearly 5-fold improvement in hot-electron injection efficiency as compared to a non-Al device, with the hot-electron lifetimes extending to >2 ps in devices photoexcited with fluence of 0.1 mJ cm-2. The use of an Al film also enhances the photocatalytic yield of H2O2 more than 3-fold in a visible-light-driven reactor. Altogether, we show that the critical coupling of Al films to Au nanoparticles is a low-cost, lithography-free method for improving visible-light capture, extending hot-carrier lifetimes, and ultimately increasing the rate of in situ H2O2 generation.

A general synthesis approach for supported bimetallic nanoparticles via surface inorganometallic chemistry.

The synthesis of ultrasmall supported bimetallic nanoparticles (between 1 and 3 nanometers in diameter) with well-defined stoichiometry and intimacy between constituent metals remains a substantial challenge. We synthesized 10 different supported bimetallic nanoparticles via surface inorganometallic chemistry by decomposing and reducing surface-adsorbed heterometallic double complex salts, which are readily obtained upon sequential adsorption of target cations and anions on a silica substrate. For example, adsorption of tetraamminepalladium(II) [Pd(NH3)4 2+] followed by adsorption of tetrachloroplatinate [PtCl4 2-] was used to form palladium-platinum (Pd-Pt) nanoparticles. These supported bimetallic nanoparticles show enhanced catalytic performance in acetylene selective hydrogenation, which clearly demonstrates a synergistic effect between constituent metals.

Constructing Hierarchical Porous Zeolites via Kinetic Regulation.

Zeolites are crystalline inorganic solids with microporous structures, having widespread applications in the fields of catalysis, separation, adsorption, microelectronics, and medical diagnosis. A major drawback of zeolites is the mass transfer limitation due to the small size of the micropores (less than 1 nm). Numerous efforts have been dedicated to integrating mesopores with the microporous zeolite structures by using templating and/or destructive approaches. Here we provide a new strategy for hierarchical pore size zeolite synthesis, without using supramolecular or hard templates. The branching epitaxial growth behavior, as a result of aluminum-zoning, contributes to the formation of the hierarchical porous zeolite structures.

Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts.

Identification and characterization of catalytic active sites are the prerequisites for an atomic-level understanding of the catalytic mechanism and rational design of high-performance heterogeneous catalysts. Indirect evidence in recent reports suggests that platinum (Pt) single atoms are exceptionally active catalytic sites. We demonstrate that infrared spectroscopy can be a fast and convenient characterization method with which to directly distinguish and quantify Pt single atoms from nanoparticles. In addition, we directly observe that only Pt nanoparticles show activity for carbon monoxide (CO) oxidation and water-gas shift at low temperatures, whereas Pt single atoms behave as spectators. The lack of catalytic activity of Pt single atoms can be partly attributed to the strong binding of CO molecules.

Adhesion and Atomic Structures of Gold on Ceria Nanostructures: The Role of Surface Structure and Oxidation State of Ceria Supports.

We report an aberration-corrected electron microscopy analysis of the adhesion and atomic structures of gold nanoparticle catalysts supported on ceria nanocubes and nanorods. Under oxidative conditions, the as-prepared gold nanoparticles on the ceria nanocubes have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod supports. Under the reducing conditions of water-gas shift reaction, the extended gold atom layers and rafts vanish. In addition, the gold particles on the nanocubes change in morphology and increase in size while those on the nanorods are almost unchanged. The size, morphology, and atomic interface structures of gold strongly depend on the surface structures of ceria supports ((100) surface versus (111) surface) and the reaction environment (reductive versus oxidative). These findings provide insights into the deactivation mechanisms and the shape-dependent catalysis of oxide supported metal catalysts.

Microwave synthesis of microstructured and nanostructured metal chalcogenides from elemental precursors in phosphonium ionic liquids.

We describe a general approach for the synthesis of micro-/nanostructured metal chalcogenides from elemental precursors. The excellent solubility of sulfur, selenium, and tellurium in phosphonium ionic liquids promotes fast reactions between chalcogens and various metal powders upon microwave heating, giving crystalline products. This approach is green, universal, and scalable.

Fluorescence upconversion microbarcodes for multiplexed biological detection: nucleic acid encoding.

Fluoride rare-earth-doped upconversion microbarcodes have been successfully developed for multiplexed signaling and nucleic-acid encoding. This kind of novel barcode material can be used for rapid and sensitive analysis of nucleic acids and antigens, which would have many potential applications in clinical, food, and environment detection.

CO2-mediated synthesis of ZnO nanorods and their application in sensing ethanol vapor.

High-purity ZnO nanorods have been synthesized via a two-step route using zinc acetate as a precursor without any surfactant and additive. In this method, ZnCO3 fibers were first formed in the CO2-ethanol solution, which directed the formation of ZnO nanorods by subsequent treatment in KOH aqueous solution. The as-prepared nanorods were fully characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and Fourier transform Infrared spectroscopy. It was found that the as-obtained ZnO nanorods were single crystals with uniform diameter around 150 nm and length of 4 microm. The nanorod crystals were prismatic with hexagonal cross sections, consistent with the wurtzite lattice structure. Moreover, the sensing properties of the as-prepared ZnO nanorods were also investigated. It was demonstrated that they exhibited good performance for detecting ethanol vapor even at 380 and 250 degrees C.

Surfactant-free synthesis of Bi2Te3-Te micro-nano heterostructure with enhanced thermoelectric figure of merit.

An ideal thermoelectric material would be a semiconductor with high electrical conductivity and relatively low thermal conductivity: an "electron crystal, phonon glass". Introducing nanoscale heterostructures into the bulk TE matrix is one way of achieving this intuitively anomalous electron/phonon transport behavior. The heterostructured interfaces are expected to play a significant role in phonon scattering to reduce thermal conductivity and in the energy-dependent scattering of electrical carriers to improve the Seebeck coefficient. A nanoparticle building block assembly approach is plausible to fabricate three-dimensional heterostructured materials on a bulk commercial scale. However, a key problem in applying this strategy is the possible negative impact on TE performance of organic residue from the nanoparticle capping ligands. Herein, we report a wet chemical, surfactant-free, low-temperature, and easily up-scalable strategy for the synthesis of nanoscale heterophase Bi(2)Te(3)-Te via a galvanic replacement reaction. The micro-nano heterostructured material is fabricated bottom-up, by mixing the heterophase with commercial Bi(2)Te(3). This unique structure shows an enhanced zT value of ∼0.4 at room temperature. This heterostructure has one of the highest figures of merit among bismuth telluride systems yet achieved by a wet chemical bottom-up assembly. In addition, it shows a 40% enhancement of the figure of merit over our lab-made material without nanoscale heterostructures. This enhancement is mainly due to the decrease in the thermal conductivity while maintaining the power factor. Overall, this cost-efficient and room-temperature synthesis methodology provides the potential for further improvement and large-scale thermoelectric applications.

Shape controlled synthesis of palladium nanocrystals by combination of oleylamine and alkylammonium alkylcarbamate and their catalytic activity.

The shape of Pd nanocrystals (NCs) can be controlled by combination of oleylamine (OAm) and alkylammonium alkylcarbamate (AAAC), and Pd spheres, tetrahedra and multipods have been synthesized. The multipods and tetrahedra are much more active than the spheres for hydrogenation reactions.

Arginine-mediated synthesis of highly efficient catalysts for transfer hydrogenations of ketones.

Palladium-hydrotalcite catalysts were prepared by immobilizing Pd(2+) on hydrotalcite (HT) via an amino acid, arginine (Arg), followed by reduction with NaBH(4) at room temperature. The resulting composite was characterized by different techniques. X-ray photoelectron spectroscopy analysis showed that the loaded Pd on hydrotalcite mainly existed in the form of Pd(0), and distributed uniformly on the support with particle size around 4 nm, as confirmed by transmission electron microscopy examination. The HT-Arg-Pd composites were used to catalyze transfer hydrogenation of aromatic ketones, which exhibited high efficiency for this kind of reaction. It was demonstrated that arginine played an important role in the high activity and stability of the catalyst, which not only mediated Pd nanoparticles to be immobilized on the HT support firmly but also promoted the transfer hydrogenation reactions.

The immobilization of glycidyl-group-containing ionic liquids and its application in CO2 cycloaddition reactions.

Covalent immobilization of glycidyl-group-containing ionic liquids (ILs) on organic and inorganic supports with functional surfaces was achieved, based on the fact that the glycidyl group can actively react with almost all nucleophilic, electrophilic, neutral, and free-radical species. By using polymer spheres with amino- and carboxyl-group-functionalized surfaces as organic supports and silicas (including SBA15 and silica gel) with amino groups attached as inorganic supports, the ionic liquid 1-glycidyl-butylimidazolium chloride was successfully grafted onto these polymer and silica supports, respectively, through reactions between the glycidyl group in the IL and the polar groups on the support surfaces. The resultant samples were examined by transmission electron microscopy, solid-state (13)C NMR spectroscopy, IR spectroscopy, and ion chromatography. The activities of these resultant polymer- and silica-based catalysts were investigated for CO(2) cycloaddition reactions with epoxides. It was demonstrated that these catalysts could effectively catalyze CO(2) cycloaddition. In particular, the polymer supports generated synergistic effects with the IL in the coupling reaction of CO(2) with propylene oxide, and the turnover frequency could reach about 1700 h(-1) when the IL attached to the NH(2)-functionalized polymer was used as the catalyst.

Study on the anatase to rutile phase transformation and controlled synthesis of rutile nanocrystals with the assistance of ionic liquid.

We developed a route to synthesize rutile TiO(2) nanocrystals (NCs) with the assistance of 1-butyl-3-methylimidazolium chloride (bmim(+)Cl(-)). The phase transformation from anatase to rutile phase was investigated, and a simple model to describe the phase transformation process was proposed considering that the nucleation and growth of rutile phase were determined by the aggregation manner of anatase NCs and Ostwald ripening process, respectively. It was demonstrated that the surfactant-like nature of the IL used was crucial for controlling the crystallization process via controlling the aggregation manner of the NCs. The phase, shape, and size of TiO(2) NCs could be tuned by the controlling the operating conditions, such as temperature, solution acidity, and reactant concentration of the bmim(+)Cl(-)/TiCl(4)/H(2)O reaction system. Phase-pure rutile multipods and 1D nanorods with different sizes were controllably obtained.

Dispersion of graphene sheets in ionic liquid [bmim][PF6] stabilized by an ionic liquid polymer.

Dispersion of graphene sheets in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was successfully achieved with the aid of a polymerized ionic liquid (PIL).