Heteroatoms-Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation.

As a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over-hydrogenation. Herein, we develop an efficient catalytic system based on single-atom Pd catalysts supported on boron-containing amorphous zeolites (Pd/AZ-B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ-B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h-1 and demonstrating 95% selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom-free amorphous zeolite-anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73% and 15%, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.

Honeycomb-Structured IrOx Foam Platelets as the Building Block of Anode Catalyst Layer in PEM Water Electrolyzer.

Achieving robust long-term durability with high catalytic activity at low iridium loading remains one of great challenges for proton exchange membrane water electrolyzer (PEMWE). Herein, we report the low-temperature synthesis of iridium oxide foam platelets comprising edge-sharing IrO6 octahedral honeycomb framework, and demonstrate the structural advantages of this material for multilevel tuning of anodic catalyst layer across atomic-to-microscopic scales for PEMWE. The integration of IrO6 octahedral honeycomb framework, foam-like texture and platelet morphology into a single material system assures the generation and exposure of highly active and stable iridium catalytic sites for the oxygen evolution reaction (OER), while facilitating the reduction of both mass transport loss and electronic resistance of catalyst layer. As a proof of concept, the membrane electrode assembly in single-cell PEMWE based on honeycomb-structured IrOx foam platelets, with a low iridium loading (~0.3 mgIr/cm2), is demonstrated to exhibit high catalytic activity at ampere-level current densities and to remain stable for more than 2000 hours.

Polymorphic Covalent Organic Frameworks: Molecularly Defined Pore Structures and Iodine Adsorption Property.

Radioactive iodine-capturing materials are urgently needed for the emerging challenges in nuclear waste disposal. The various pore structures of covalent organic frameworks (COFs) render them promising candidates for efficient iodine adsorption. However, the detailed structure-property relationship of COFs in iodine adsorption remains elusive. Herein, two polymorphic COFs with significantly different crystalline structures are obtained based on the same building blocks with varied molecular ratios. The two COFs both have high crystallinity, high specific surface area, and excellent chemical and thermal stability. Compared with the [C4+C4] topology (PyT-2) with an AA stacking form, the [C4+C2] topology (PyT-1) with an AB stacking form has more twisted pore channels and complex ink-bottle pores. At ambient conditions, PyT-1 and PyT-2 both exhibit good adsorption properties for iodine capture either in a gaseous or liquid medium. Remarkably, PyT-1 presents an excellent maximum adsorption capacity (0.635 g g-1), and the adsorption limit of PyT-2 is 0.445 g g-1 in an n-hexane solution with an iodine concentration of 400 mg L-1, which is highly comparable to the state-of-the-art iodine absorption performance. This study provides a guide for the future molecular design strategy toward novel iodine adsorbents.

Electrocatalytic Water Oxidation Activity-Stability Maps for Perovskite Oxides Containing 3d, 4d and 5d Transition Metals.

Improving catalytic activity without loss of catalytic stability is one of the core goals in search of low-iridium-content oxygen evolution electrocatalysts under acidic conditions. Here, we synthesize a family of 66 SrBO3 perovskite oxides (B=Ti, Ru, Ir) with different Ti : Ru : Ir atomic ratios and construct catalytic activity-stability maps over composition variation. The maps classify the multicomponent perovskites into chemical groups with distinct catalytic activity and stability for acidic oxygen evolution reaction, and highlights a chemical region where high catalytic activity and stability are achieved simultaneously at a relatively low iridium level. By quantifying the extent of hybridization of mixed transition metal 3d-4d-5d and oxygen 2p orbitals for multicomponent perovskites, we demonstrate this complex interplay between 3d-4d-5d metals and oxygen atoms in governing the trends in both activity and stability as well as in determining the catalytic mechanism involving lattice oxygen or not.

Encapsulation of Palladium Carbide Subnanometric Species in Zeolite Boosts Highly Selective Semihydrogenation of Alkynes.

The selective hydrogenation of alkynes to alkenes is a crucial step in the synthesis of fine chemicals. However, the widely utilized palladium (Pd)-based catalysts often suffer from poor selectivity. In this work, we demonstrate a carbonization-reduction method to create palladium carbide subnanometric species within pure silicate MFI zeolite. The carbon species can modify the electronic and steric characteristics of Pd species by forming the predominant Pd-C4 structure and, meanwhile, facilitate the desorption of alkenes by forming the Si-O-C structure with zeolite framework, as validated by the state-of-the-art characterizations and theoretical calculations. The developed catalyst shows superior performance in the selective hydrogenation of alkynes over mild conditions (298 K, 2 bar H2 ), with 99 % selectivity to styrene at a complete conversion of phenylacetylene. In contrast, the zeolite-encapsulated carbon-free Pd catalyst and the commercial Lindlar catalyst show only 15 % and 14 % selectivity to styrene, respectively, under identical reaction conditions. The zeolite-confined Pd-carbide subnanoclusters promise their superior properties in semihydrogenation of alkynes.

Macrocyclic Arenes-Based Conjugated Macrocycle Polymers for Highly Selective CO2 Capture and Iodine Adsorption.

Incorporating synthetic macrocycles with unique structures and distinct conformations into conjugated macrocycle polymers (CMPs) can endow the resulting materials with great potentials in gas uptake and pollutant adsorption. Here, four CMPs (CMP-n, n=1-4) capable of reversibly capturing iodine and efficiently separating carbon dioxide are constructed from per-triflate functionalized leaning tower[6]arene (LT6-OTf) and [2]biphenyl-extended pillar[6]arene (BpP6-OTf) via Pd-catalyzed Sonogashira-Hagihara cross-coupling reaction. Intriguingly, owing to the appropriate cavity size of LT6-OTf and the numerous aromatic rings in the framework, the newly designed CMP-4 possesses an outstanding I2 affinity with a large uptake capacity of 208 wt % in vapor and a great removal efficiency of 94 % in aqueous solutions. To our surprise, with no capacity to accommodate nitrogen, CMP-2 constructed from BpP6-OTf is able to specifically capture carbon dioxide at ambient conditions.

An Azine-Linked Covalent Organic Framework: Synthesis, Characterization and Efficient Gas Storage.

A azine-linked covalent organic framework, COF-JLU2, was designed and synthesized by condensation of hydrazine hydrate and 1,3,5-triformylphloroglucinol under solvothermal conditions for the first time. The new covalent organic framework material combines permanent micropores, high crystallinity, good thermal and chemical stability, and abundant heteroatom activated sites in the skeleton. COF-JLU2 possesses a moderate BET surface area of over 410 m(2) g(-1) with a pore volume of 0.56 cm(3) g(-1) . Specifically, COF-JLU2 displays remarkable carbon dioxide uptake (up to 217 mg g(-1) ) and methane uptake (38 mg g(-1) ) at 273 K and 1 bar, as well as high CO2 /N2 (77) selectivity. Furthermore, we further highlight that it exhibits a higher hydrogen storage capacity (16 mg g(-1) ) than those of reported COFs at 77 K and 1 bar.

A general route to hollow mesoporous rare-earth silicate nanospheres as a catalyst support.

Hollow mesoporous structures have recently aroused intense research interest owing to their unique structural features. Herein, an effective and precisely controlled synthesis of hollow rare-earth silicate spheres with mesoporous shells is reported for the first time, produced by a simple hydrothermal method, using silica spheres as the silica precursors. The as-prepared hollow rare-earth silicate spheres have large specific surface area, high pore volume, and controllable structure parameters. The results demonstrate that the selection of the chelating reagent plays critical roles in forming the hollow mesoporous structures. In addition, a simple and low-energy-consuming approach to synthesize highly stable and dispersive gold nanoparticle-yttrium silicate (AuNPs/YSiO) hollow nanocomposites has also been developed. The reduction of 4-nitrophenol with AuNPs/YSiO hollow nanocomposites as the catalyst has clearly demonstrated that the hollow rare-earth silicate spheres are good carriers for Au nanoparticles. This strategy can be extended as a general approach to prepare multifunctional yolk-shell structures with diverse compositions and morphologies simply by replacing silica spheres with silica-coated nanocomposites.

Nitrogen-doped carbon material NCM-T heterogeneously catalyzed liquid-phase hydrogenation of nitrobenzene to aniline.

As an important chemical intermediate, aniline is primarily produced industrially through catalytic hydrogenation of nitrobenzene. Herein, a series of nitrogen-doped carbon materials (referred to as NCM-T, with T denoting the roasting temperature (°C)) were prepared through high-temperature roasting of sucrose and melamine for the heterogeneous catalytic liquid-phase hydrogenation of nitrobenzene to aniline. A preliminary study of the involved reaction mechanism was performed by combining the results of material characterisation and catalyst evaluation. Experimental results showed that the graphitic N content and the defective sites simultaneously affected the performance of NCM-T in catalysing the hydrazine hydrate reduction in the nitrobenzene hydrogenation reaction. The catalyst NCM-800 was reacted in an ethanol solution with hydrazine hydrate as the reducing agent at 80 °C for 5 h. Notably, the nitrobenzene conversion rate was up to 94%, and the aniline selectivity was 100%. The turnover frequency (TOF) could reach up to 7.9 mol g-1 h-1, and after five recycling cycles, only a small loss of catalytic activity was observed. This shows that the prepared catalyst is a recyclable catalyst that can be used for reducing the nitrobenzene from hydrazine hydrate to aniline.

Optimizing Edge Active Sites via Intrinsic In-Plane Iridium Deficiency in Layered Iridium Oxides for Oxygen Evolution Electrocatalysis.

Improving catalytic activity of surface iridium sites without compromising catalytic stability is the core task of designing more efficient electrocatalysts for oxygen evolution reaction (OER) in acid. This work presents phase transition of a bulk layered iridate Na2IrO3 in acid solution at room temperature, and subsequent exfoliation to produce 2D iridium oxide nanosheets with around 4 nm thickness. The nanosheets consist of OH-terminated, honeycomb-type layers of edge-sharing IrO6 octahedral framework with intrinsic in-plane iridium deficiency. The nanosheet material is among the most active Ir-based catalysts reported for acidic OER and gives an iridium mass activity improvement up to a factor of 16.5 over rutile IrO2 nanoparticles. The material also exhibits good catalytic and structural stability and retains the catalytic activity for more than 1300 h. The combined experimental and theoretical results demonstrate that edge Ir sites of the layer are active centers for OER, with structural hydroxyl groups participating in the catalytic cycle of OER via a non-traditional adsorbate evolution mechanism. The existence of intrinsic in-plane iridium deficiency is the key to building a unique local environment of edge active sites that have optimal surface oxygen adsorption properties and thereby high catalytic activity.

Supported IrO2 Nanocatalyst with Multilayered Structure for Proton Exchange Membrane Water Electrolysis.

The design of a low-iridium-loading anode catalyst layer with high activity and durability is a key challenge for a proton exchange membrane water electrolyzer (PEMWE). Here, the synthesis of a novel supported IrO2 nanocatalyst with a tri-layered structure, dubbed IrO2@TaOx@TaB that is composed of ultrasmall IrO2 nanoparticles anchored on amorphous TaOx overlayer of TaB nanorods is reported. The composite electrocatalyst shows great activity and stability toward the oxygen evolution reaction (OER) in acid, thanks to its dual-interface structural feature. The electronic interaction in IrO2/TaOx interface can regulate the coverage of surface hydroxyl groups, the Ir3+/ Ir4+ ratio, and the redox peak potential of IrO2 for enhancing OER activity, while the dense TaOx overlayer can prevent further oxidation of TaB substrate and stabilize the IrO2 catalytic layers for improving structural stability during OER. The IrO2@TaOx@TaB can be used to fabricate an anode catalyst layer of PEMWE with an iridium-loading as low as 0.26 mg cm-2. The low-iridium-loading PEMWE delivers high current densities at low cell voltages (e.g., 3.9 A cm-2@2.0 V), and gives excellent activity retention for more than 1500 h at 2.0 A cm-2 current density.

Porous titania with heavily self-doped Ti3+ for specific sensing of CO at room temperature.

Semiconductor-based sensors have played an important role in efficient detection of combustible, flammable, and toxic gases, but they usually need to operate at elevated temperatures (200 °C or higher). Although reducing the operation temperature down to room temperature is of practical significance, it is still a huge challenge to fabricate room temperature sensors with a low cost. Here we show a novel "self-doping" strategy to overcome simultaneously both difficulties of "high resistance" and "low reaction rate", which have always been encountered for room-temperature operation of semiconductor-based sensors. In particular, a porous crystalline titania with heavily self-doped Ti(3+) species has been prepared by using a porous amorphous TiO2 and urea as the starting materials. The resulting Ti(3+) self-doped TiO2 material serves as an efficient room-temperature gas-sensing material for specific CO detection with fast response/recovery. The self-dopant (Ti(3+)) in the titania material has proved to decrease the resistance of TiO2 significantly on the one hand and to increase the chemisorbed oxygen species substantially, thus enhancing the surface reaction activity on the other. Such a self-doping concept is anticipated to give a fresh impetus to rational design of room-temperature sensing devices with low costs.

A Highly Active, Long-Lived Oxygen Evolution Electrocatalyst Derived from Open-Framework Iridates.

The acidic oxygen evolution reaction underpins several important electrical-to-chemical energy conversions, and this energy-intensive process relies industrially on iridium-based electrocatalysts. Here, phase-selective synthesis of metastable strontium iridates with open-framework structure and their unexpected transformation into a highly active, ultrastable oxygen evolution nano-electrocatalyst are presented. This transformation involves two major steps: Sr2+ /H+ ion exchange in acid and in situ structural rearrangement under electrocatalysis conditions. Unlike its dense perovskite-structured polymorphs, the open-framework iridates have the ability to undergo rapid proton exchange in acid without framework amorphization. The resulting protonated iridates further reconstruct into ultrasmall, surface-hydroxylated, (200) crystal plane-oriented rutile nanocatalyst, instead of the common amorphous IrOx Hy phase, during acidic oxygen evolution. Such microstructural characteristics are found to benefit both the oxidation of hydroxyls and the formation of OO bonds in electrocatalytic cycle. As a result, the open-framework iridate derived nanocatalyst gives a comparable catalytic activity to the most active iridium-based oxygen evolution electrocatalysts in acid, and retains its catalytic activity for more than 1000 h.

Nano-metal diborides-supported anode catalyst with strongly coupled TaOx/IrO2 catalytic layer for low-iridium-loading proton exchange membrane electrolyzer.

The sluggish kinetics of oxygen evolution reaction (OER) and high iridium loading in catalyst coated membrane (CCM) are the key challenges for practical proton exchange membrane water electrolyzer (PEMWE). Herein, we demonstrate high-surface-area nano-metal diborides as promising supports of iridium-based OER nanocatalysts for realizing efficient, low-iridium-loading PEMWE. Nano-metal diborides are prepared by a novel disulphide-to-diboride transition route, in which the entropy contribution to the Gibbs free energy by generation of gaseous sulfur-containing products plays a crucial role. The nano-metal diborides, TaB2 in particular, are investigated as the support of IrO2 nanocatalysts, which finally forms a TaOx/IrO2 heterojunction catalytic layer on TaB2 surface. Multiple advantageous properties are achieved simultaneously by the resulting composite material (denoted as IrO2@TaB2), including high electrical conductivity, improved iridium mass activity and enhanced corrosion resistance. As a consequence, the IrO2@TaB2 can be used to fabricate the membrane electrode with a low iridium loading of 0.15 mg cm-2, and to give an excellent catalytic performance (3.06 A cm-2@2.0 V@80 oC) in PEMWE-the one that is usually inaccessible by unsupported Ir-based nanocatalysts and the vast majority of existing supported Ir-based catalysts at such a low iridium loading.

Switching between classical/nonclassical crystallization pathways of TS-1 zeolite: implication on titanium distribution and catalysis.

In the MFI zeolite crystallization process, the classical crystallization mechanism based upon the addition of silica species is often concomitant with the nonclassical route that is characteristic of the attachment of silica nanoparticle precursors. However, the factors that govern the preferences for each mechanism remain unclear. In this work, we present the impact of switching between these two crystallization pathways on the active sites and the resulting catalytic performance of the titanosilicate TS-1 zeolite. By controlling the self-assembled precursor structures in the early crystallization stage which are mediated by the Ti and H2O in the reaction system, we could achieve the preferred modes of crystal growth of the TS-1 zeolite. We indicate that by directing the predominant crystallization path from the classical to the nonclassical route, it is possible to generate more stable bridging peroxo species upon reaction with hydrogen peroxide, as confirmed by 17O solid-state nuclear magnetic resonance spectroscopy, thus substantially increasing the catalytic performance of the resulting TS-1 for olefin epoxidation.

Controllable synthesis and photoluminescence of single-crystalline BaHfO3 hollow micro- and nanospheres.

This paper presents a facile hydrothermal route to synthesize monodispersive and single-crystalline BaHfO(3) hollow micro- and nanospheres in a concentrated basic environment. The hollow spheres were size tunable from submicrometer to nanoscale by simply adjusting the base concentration at a suitable temperature. The base concentration played the key role on forming BaHfO(3) hollow spheres. Detailed investigations on base concentration, reaction temperature, and duration indicated that the formation of BaHfO(3) hollow spheres was driven by Ostwald ripening process. Because of the abundance of defects, the as-prepared BaHfO(3) hollow nanospheres exhibited a blue light emission under UV-light excitation at room temperature. Calcination led to the photoluminescence declination due to the decrease of defects.

Electron donation of non-oxide supports boosts O2 activation on nano-platinum catalysts.

Activation of O2 is a critical step in heterogeneous catalytic oxidation. Here, the concept of increased electron donors induced by nitrogen vacancy is adopted to propose an efficient strategy to develop highly active and stable catalysts for molecular O2 activation. Carbon nitride with nitrogen vacancies is prepared to serve as a support as well as electron sink to construct a synergistic catalyst with Pt nanoparticles. Extensive characterizations combined with the first-principles calculations reveal that nitrogen vacancies with excess electrons could effectively stabilize metallic Pt nanoparticles by strong p-d coupling. The Pt atoms and the dangling carbon atoms surround the vacancy can synergistically donate electrons to the antibonding orbital of the adsorbed O2. This synergistic catalyst shows great enhancement of catalytic performance and durability in toluene oxidation. The introduction of electron-rich non-oxide substrate is an innovative strategy to develop active Pt-based oxidation catalysts, which could be conceivably extended to a variety of metal-based catalysts for catalytic oxidation.

Exsolution of Iron Oxide on LaFeO3 Perovskite: A Robust Heterostructured Support for Constructing Self-Adjustable Pt-Based Room-Temperature CO Oxidation Catalysts.

Constructing highly active and stable surface sites for O2 activation is essential to lower the barrier of Pt-based catalysts for CO oxidation. Although a few active Pt-metal oxide interfaces have been reported, questions about the stability of these sites under the long-term storage and operation remain unresolved. Here, based on developing a robust FeOx/LaFeO3 heterostructure as a support, we constructed stable Pt-support interfaces to achieve highly active CO oxidation at room temperature. Even after it is kept in the air for more than 6 months, the catalyst (without pretreatment) still maintains the high activity like a fresh one, which is superior to metal hydroxide-Pt interfaces, and meets the requirements of long-term storage for emergency use. In situ characterizations and systematic reaction results showed that CO oxidation occurs through an alternative mechanism, which is triggered by intrinsic reactants and self-adjusted to a more active interface in the reaction process. Theoretical calculations and 57Fe Mössbauer spectra revealed that abundant cation vacancies significantly increase the activity of surface oxygen species and should be responsible for this unique process. This work demonstrates an alternative concept to fabricate robust and highly active Pt-based catalysts for catalytic oxidation.

Polyoxometalate-viologen photochromic hybrids for rapid solar ultraviolet light detection, photoluminescence-based UV probing and inkless and erasable printing.

In this work, a new crystalline polyoxometalate-viologen hybrid, (Pbpy)(Me2NH2)3[PW11ZnO40] (1: Pbpy = 1,1'-[1,4-phenylenebis-(methylene)]bis(4,4'-bipyridinium)), has been synthesized. It showed efficient ultraviolet light detection ability with an obvious colour change from pale yellow to blue and fast response with ultraviolet intensity as low as 0.006 mW cm-2 in narrow-band UV regions. The POM-viologen-based film of 1 has also been readily prepared on quartz substrates using a drop casting method and could exhibit different levels of colour changes under sunlight irradiation at different local times on a sunny day, indicating its potential to be used as a portable device for solar ultraviolet light detection. Ultraviolet light detection is not only reflected in colour changes, but also accompanies the photoluminescence phenomenon. The fluorescence intensity decreased with the increase of UV intensity, and when irradiated with an ultraviolet xenon lamp (8 mW cm-2) for about 5 min, the fluorescence intensity was almost completely quenched. The compound has the potential to achieve fluorescence based UV probing. The powdered sample of compound 1 could also be deposited in paper simply by coating it with a solution of ethanol. The paper can be used as an inkless and erasable print medium, which was found to remain clear for 11 d in the dark under an ambient atmosphere and was also reusable when erased.

Construction of fluorescence active MOFs with symmetrical and conformationally rigid N-2-aryl-triazole ligands.

1,4-Bis-triazole-substituted arene (NAT) was designed and synthesized for the construction of metal organic frameworks. Unlike the tri-phenyl analogs, which give a twisted conformation between three benzene rings due to the A-1,3 repulsion, the NAT-ligand gave the energetically favored co-planar conformation with the strong fluorescence emission. With this ligand, two new MOFs, NAT-MOF-Cd (2,3,4-c) and NAT-MOF-Cu (4-c), were successfully obtained with the structure confirmed by X-ray. With the six-coordinated Cd(ii) cluster, an interesting metal-ligand coordination and H-bonding hybridized porous polymeric structures were observed. In contrast, a typical Cu(ii) paddle wheel coordination was obtained with NAT and Cu, giving a new MOF structure with moderate stability in aqueous solution from pH 1-11 for 24 hours, which suggests a promising future for applications in fluorescence sensing and photocatalysis.