Divalent Oxidation State Ni as an Active Intermediate in Prussian Blue Analogues for Electrocatalytic Urea Oxidation.

Urea degradation is one of the most crucial links in the natural nitrogen cycle. Exploring the real active species in the urea electro-oxidation process is of great significance for understanding the urea electro-oxidation mechanism and designing catalysts. A highly active and stable Prussian blue analogue catalyst (PBA@NiFe/NF) loaded on nickel foam was synthesized for electro-oxidation of urea. In situ Raman spectra revealed that Ni in PBA@NiFe/NF was able to maintain a stable divalent nickel (Ni(II)) state for up to 3.5 h during the initial urea oxidation process, which is rarely reported in previous research studies. In addition, with the participation of iron, the Ni-Fe bimetallic center significantly improves the electro-oxidation of urea. Our work provides a new idea for prolonging the Ni(II) activity in electrocatalytic oxidation of urea.

Vibration-driven Reduction of CO2 to Acetate with 100 % Selectivity by SnS Nanobelt Piezocatalysts.

Converting CO2 into high-value C2 chemicals such as acetate with high selectivity and efficiency is a critical issue in renewable energy storage. Herein, for the first time we present a vibration-driven piezocatalysis with tin(II) monosulfide (SnS) nanobelts for conversion of CO2 to acetate with 100 % selectivity, and the highest production rate (2.21 mM h-1 ) compared with reported catalysts. Mechanism analysis reveal that the polarized charges triggered by periodic mechanical vibration promote the adsorption and activation of CO2 . The electron transfer can be facilitated due to built-in electric field, decreased band gap and work function of SnS under stress. Remarkably, reduced distance between active sites leads to charge enrichment on Sn sites, promoting the C-C coupling, reducing the energy barriers of the rate determining step. It puts forward a bran-new strategy for converting CO2 into high-value C2 products with efficient, low-cost and environment-friendly piezocatalysis utilizing mechanical energy.

Visualizing Assembly Dynamics of All-Liquid 3D Architectures.

To better exploit all-liquid 3D architectures, it is essential to understand dynamic processes that occur during printing one liquid in a second immiscible liquid. Here, the interfacial assembly and transition of 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H6 TPPS) over time provides an opportunity to monitor the interfacial behavior of nanoparticle surfactants (NPSs) during all-liquid printing. The formation of J-aggregates of H4 TPPS2- at the interface and the interfacial conversion of the J-aggregates of H4 TPPS2- to H-aggregates of H2 TPPS4- is demonstrated by interfacial rheology and in situ atomic force microscopy. Equally important are the chromogenic changes that are characteristic of the state of aggregation, where J-aggregates are green in color and H-aggregates are red in color. In all-liquid 3D printed structures, the conversion in the aggregate state with time is reflected in a spatially varying change in the color, providing a simple, direct means of assessing the aggregation state of the molecules and the mechanical properties of the assemblies, linking a macroscopic observable (color) to mechanical properties.

Synthesis of Diarylselenides through Rh-Catalyzed Direct Diarylation of Elemental Selenium with Benzamides.

Diarylselenides are a representative class of molecules in organoselenium compounds. We herein report a Rh-catalyzed direct diarylation of selenium with benzamide derivatives. The use of elemental selenium as the Se source is intriguing in terms of atom economy, cost, stability, and handling. A series of diarylselenides with amide moieties were readily accessible through directed C-H activation. The intermediacy of electrophilic Se(IV) species was indicated by control experiments.

Construction of Perylene-based Amphiphilic Micelle and Its Efficient Adsorption and In Situ Photodegradation of Bisphenol A in Aqueous Solution.

Low mass-transfer efficiency and reaction-driving force make it difficult to realize thorough purification in traditional low-concentration pollutant treatments. Herein, we propose an "adsorption/catalysis in situ" perylene based bifunctional micelle for efficient, accurate and rapid adsorption and catalytic degradation of low-concentration bisphenol A (BPA). They show super-fast (within 10 s), high capacity (448 mg g-1 ) and selectivity for BPA adsorption, due to π-π, hydrophobic interactions and hydrogen bonding. The BPA degradation efficiency improves by up to 8 times after forming micelles compared with simple perylene nanorods, which is primarily due to the superior mass-transfer from adsorption. Moreover, self-assembly can optimize the stacking of the perylene moieties and facilitate charge transfer in micelle, and the regular π-π stacking of inside perylene units enhances the response to visible light, resulting in high catalytic capacity and good cycling stability.

SuFEx-Enabled Elastic Polysulfates for Efficient Removal of Radioactive Iodomethane and Polar Aprotic Organics through Weak Intermolecular Forces.

Capturing radioactive iodomethane and its vapors is a major challenge due to its low adsorption capacity. Herein, we have developed for the first time a pyridine-entrapped elastic crosslinked polysulfate gel (pyridine/TPC-cPS) as an efficient absorbent for iodomethane capture. Each pyridine-encased TPC-cPS network cell acts as a mini-reactor for salt formation between pyridine and iodomethane. The yield reaches up to 96.65 % and traps saturated iodomethane vapor of 1.573 g gpyridine/TPC-cPS -1 (equivalent to 18.103 g gTPC-cPS -1 ), which is the highest capacity reported to date. Both experiments and molecular dynamics simulations reveal that the unusual adsorption of polysulfate for polar aprotic organics can be attributed to the fact that the electrostatic interactions between the polar group (O=S=O) in the polymer backbone and the polar groups in the organic molecules fixed the solvent in the polymer matrix, while the van der Waals forces between the nonpolar groups in the polymer and molecules induced swelling.

Synthesis of Benzoisoselenazolones via Rh(III)-Catalyzed Direct Annulative Selenation by Using Elemental Selenium.

Isoselenazolone derivatives have attracted significant research interest because of their potent therapeutic activities and indispensable applications in organic synthesis. Efficient construction of functionalized isoselenazolone scaffolds is still challenging, and thus new synthetic approaches with improved operational simplicity have been of particular interest. In this manuscript, we introduce a rhodium-catalyzed direct selenium annulation by using stable and tractable elemental selenium. A series of benzamides as well as acrylamides were successfully coupled with selenium under mild reaction conditions, and the obtained isoselenazolones could be pivotal synthetic precursors for several organoselenium compounds. Based on the designed control experiments and X-ray absorption spectroscopy measurements, we propose an unprecedented selenation mechanism involving a highly electrophilic Se(IV) species as the reactive selenium donor. The reaction mechanism was further verified by a computational study.

Chiral phosphoric acid-catalyzed asymmetric dearomatization reactions.

We summarize in this review the recent development of chiral phosphoric acid (CPA)-catalyzed asymmetric dearomatization reactions. A wide array of electron-rich arenes (indoles, phenols, naphthols, benzothiophenes, benzofurans, etc.) and electron-poor arenes (pyridines, quinolines, isoquinolines, etc.) has been proved reactive towards various reaction partners in the presence of a CPA catalyst, enabling asymmetric dearomatization reactions that lead to structurally-diverse polycyclic molecules. The reactions are grouped according to the roles of the arenes in the reactions (as nucleophiles or electrophiles) and the types of reaction partners. This review closes with a personal perspective on the dynamic research area of asymmetric dearomatization reactions by CPAs.

Pt/MnO2 Nanoflowers Anchored to Boron Nitride Aerogels for Highly Efficient Enrichment and Catalytic Oxidation of Formaldehyde at Room Temperature.

The catalytic room temperature oxidation of formaldehyde (HCHO) is widely considered as a viable method for the abatement of indoor toxic HCHO pollution. Herein, Pt/MnO2 nanoflowers anchored to boron nitride aerogels (Pt/MnO2 -BN) were fabricated for the catalytic room temperature oxidation of HCHO. The three-dimensional Pt/MnO2 -BN aerogels demonstrated superior catalytic activity as a result of the improved diffusion of the reactant molecules within the porous structure. Furthermore, the porous aerogels displayed excellent HCHO adsorption capacities, which promote a rapid HCHO gas-phase concentration reduction and a subsequent complete oxidation of the adsorbed HCHO. The combined adsorption and oxidation properties of the Pt/MnO2 -BN aerogels enhance the oxidative removal of HCHO. The optimized Pt/MnO2 -BN demonstrated excellent catalytic activity toward HCHO (200 ppm) at room temperature, achieving a 96 % formaldehyde conversion after 50 min.

Visualizing Interfacial Jamming Using an Aggregation-Induced-Emission Molecular Reporter.

With the interfacial jamming of nanoparticles (NPs), a load-bearing network of NPs forms as the areal density of NPs increases, converting the assembly from a liquid-like into a solid-like assembly. Unlike vitrification, the lineal packing of the NPs in the network is denser, while the remaining NPs can remain in a liquid-like state. It is a challenge to determine the point at which the assemblies jam, since both jamming and vitrification lead to a solid-like behavior of the assemblies. Herein, we show a real-time fluorescence imaging method to probe the evolution of the interfacial dynamics of NP surfactants at the water/oil interface using aggregation-induced emission (AIE) as a reporter for the transition of the assemblies into the jammed state. The AIEgens show typical fluorescence behavior at densities at which they can move and rotate. However, when aggregation of these fluorophores occurs, the smaller intermolecular separation distance arrests rotation, and a significant enhancement in the fluorescence intensity occurs.

Surfactant-Induced Interfacial Aggregation of Porphyrins for Structuring Color-Tunable Liquids.

Locking nonequilibrium shapes of liquids into targeted architectures by interfacial jamming of nanoparticles is an emerging area in material science. 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H6 TPPS) shows three different aggregation states that present an absorption imaging platform to monitor the assembly and jamming of supramolecular polymer surfactants (SPSs) at the liquid/liquid interface. The interfacial interconversion of H6 TPPS, specifically H4 TPPS2- dissolved in water, from J- to an H-aggregation was induced by strong electrostatic interactions with amine-terminated polystyrene dissolved in toluene at the water/toluene interface. This resulted in color-tunable liquids due to interfacial jamming of the SPSs formed between H4 TPPS2- and amine-terminated polystyrene. However, the formed SPSs cannot lock in nonequilibrium shapes of liquids. In addition, a self-wrinkling behavior was observed when amphiphilic triblock copolymers of PS-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) were used to interact with H4 TPPS2- . Subsequently, the SPSs formed can lock in nonequilibrium shapes of liquids.

Nanocage-Shaped Co3- x Zrx O4 Solid-Solution Supports Loaded with Pt Nanoparticles as Effective Catalysts for the Enhancement of Toluene Oxidation.

Nanocage-shaped Co3- x Zrx O4 solid-solution supports and the corresponding platinum loaded nanocomposites, yPt/Co3- x Zrx O4 (x =0.27, 0.50, 0.69; y = 0.5, 1.0, 2.0 wt.%), are successfully fabricated via a Cu2 O nanocube hard template method and a glycol reduction method, respectively. The hollow nanocage structures obviously improve surface areas; moreover, the Zr doping forms the Co3- x Zrx O4 solid-solution supports, and the corresponding yPt/Co3- x Zrx O4 catalysts promote the enhancement of catalytic performance. Catalytic activity toward toluene combustion is enhanced for the 2.0 wt% Pt/Co2.73 Zr0.27 O4 catalyst. The catalysts are characterized using multiple techniques. Pt nanoparticles are uniformly dispersed across the Co2.73 Zr0.27 O4 nanocage surface. The 2.0 wt% Pt/Co2.73 Zr0.27 O4 catalyst exhibits the highest catalytic activity among all the samples and demonstrates good stability, with 90% toluene conversion obtained at a temperature of 165 °C. The same catalyst accomplishes full toluene oxidation at 180 °C, at a weight hourly space velocity of 36 000 mL h-1 g-1 . The apparent activation energy (Ea ) over the yPt/Co2.73 Zr0.27 O4 samples are significantly lower than those over the Co3- x Zrx O4 supports, with the 2.0 wt% Pt/Co2.73 Zr0.27 O4 catalyst exhibiting the lowest Ea value. These findings demonstrate the potential of the 2.0 wt% Pt/Co2.73 Zr0.27 O4 catalyst as a promising catalyst toward atmospheric toluene removal.

K2S2O8-HFIP synergistically promoted para-selective sp3 C-H bond diarylation of glycine esters.

A metal-free K2S2O8-HFIP synergistically promoted double Friedel-Crafts alkylation between a glycine derivative and N-substituted aniline was developed to efficiently synthesize diarylmethane derivatives with high para-selectivity. The reaction proceeded smoothly in the absence of any metal and ligand, and exhibited a good tolerance of functional groups.

Surface Engineering of g-C3 N4 by Stacked BiOBr Sheets Rich in Oxygen Vacancies for Boosting Photocatalytic Performance.

BiOBr containing surface oxygen vacancies (OVs) was prepared by a simple solvothermal method and combined with graphitic carbon nitride (g-C3 N4 ) to construct a heterojunction for photocatalytic oxidation of nitric oxide (NO) and reduction of carbon dioxide (CO2 ). The formation of the heterojunction enhanced the transfer and separation efficiency of photogenerated carriers. Furthermore, the surface OVs sufficiently exposed catalytically active sites, and enabled capture of photoexcited electrons at the surface of the catalyst. Internal recombination of photogenerated charges was also limited, which contributed to generation of more active oxygen for NO oxidation. Heterojunction and OVs worked together to form a spatial conductive network framework, which achieved 63 % NO removal, 96 % selectivity for carbonaceous products (that is, CO and CH4 ). The stability of the catalyst was confirmed by cycling experiments and X-ray diffraction and transmission electron microscopy after NO removal.

Construction of Hierarchical Hollow Co9 S8 /ZnIn2 S4 Tubular Heterostructures for Highly Efficient Solar Energy Conversion and Environmental Remediation.

Visible-light-responsive hierarchical Co9 S8 /ZnIn2 S4 tubular heterostructures are fabricated by growing 2D ZnIn2 S4 nanosheets on 1D hollow Co9 S8 nanotubes. This design combines two photoresponsive sulfide semiconductors in a stable heterojunction with a hierarchical hollow tubular structure, improving visible-light absorption, yielding a large surface area, exposing sufficient catalytically active sites, and promoting the separation and migration of photogenerated charges. The hierarchical nanotubes exhibit excellent photocatalytic H2 evolution and CrVI reduction efficiency. Under visible-light illumination, the optimized Co9 S8 /ZnIn2 S4 heterostructure provides a remarkable H2 generation rate of 9039 µmol h-1 g-1 without the use of any co-catalysts and CrVI is completely reduced in 45 min. The Co9 S8 /ZnIn2 S4 heterostructure is stable after multiple photocatalytic cycles.

3D Gold-Modified Cerium and Cobalt Oxide Catalyst on a Graphene Aerogel for Highly Efficient Catalytic Formaldehyde Oxidation.

A hard template method is used to prepare porous gold-doped cerium and cobalt oxide (Au-Cex Coy ) materials. A series of 3D Au-Ce x Coy /graphene aerogel (GA) composites is then fabricated by a facile heating method. The obtained catalysts possess a well-defined structure of ordered arrays of nanotubes and good performance in formaldehyde (HCHO) oxidation. The composition and surface elemental valence states of the catalysts are modulated by the Ce/Co molar ratio. The Au-Cex Coy catalyst and graphene oxide sheets are well compounded within 60 s through a diamine cross-linker to form 3D Au-Cex Coy /GA composites. In addition, the resulting catalyst of 3 wt% Au-Ce3 Co/GA achieves ≈55% conversion at room temperature and 100% conversion when the reaction temperature is raised at 60 °C. The synergistic effect between CeO2 and Co3 O4 promotes the migration of oxygen species and the activation of Au, which facilitates HCHO oxidation. The method used to prepare the 3D catalyst could be used to produce other catalytic materials with good replication of the template. In addition, these findings provide a simple method for rapid fabrication of catalyst/GA composites. The superior activity and stability of the 3D Au-Ce3 Co/GA catalyst make it potentially applicable in HCHO removal.

ZIF-67-Derived 3D Hollow Mesoporous Crystalline Co3 O4 Wrapped by 2D g-C3 N4 Nanosheets for Photocatalytic Removal of Nitric Oxide.

ZIF-67-derived 3D hollow mesoporous crystalline Co3 O4 wrapped by 2D graphitic carbon nitride (g-C3 N4 ) nanosheets are prepared by low temperature annealing, and are used for the photocatalytic oxidation of nitric oxide (NO) at a concentration of 600 ppb. The p-n heterojunction between Co3 O4 and g-C3 N4 forms a spatial conductive network frame and results in a broad visible light response range. The hollow mesoporous structure of Co3 O4 contributes to the circulation and adsorption of NO, and the large specific surface area exposes abundant active sites for the reaction of active species. A maximum NO degradation efficiency of 57% is achieved by adjusting the mass of the Co3 O4 precursor. Cycling tests and X-ray diffraction indicate the high stability and recyclability of the composite, making it promising in environmental purification applications.

Environmentally Robust Memristor Enabled by Lead-Free Double Perovskite for High-Performance Information Storage.

Memristors are emerging as a rising star of new computing and information storage techniques. However, the practical applications are severely challenged by their instability toward harsh conditions, including high moisture, high temperatures, fire, ionizing irradiation, and mechanical bending. In this work, for the first time, lead-free double perovskite Cs2 AgBiBr6 is utilized for environmentally robust memristors, enabling highly efficient information storage. The memory performance of the typical indium-tin-oxide/Cs2 AgBiBr6 /Au sandwich-like memristors is retained after 1000 switching cycles, 105 s of reading, and 104 times of mechanical bending, comparable to other halide perovskite memristors. Most importantly, the memristive behavior remains robust in harsh environments, including humidity up to 80%, temperatures as high as 453 K, an alcohol burner flame for 10 s, and 60 Co γ-ray irradiation for a dosage of 5 × 105 rad (SI), which is not achieved by any other memristors and commercial flash memory techniques. The realization of an environmentally robust memristor from Cs2 AgBiBr6 with a high memory performance will inspire further development of robust electronics using lead-free double perovskites.

Detection of NO2 Down to One ppb Using Ion-in-Conjugation-Inspired Polymer.

Nitrogen dioxide (NO2 ) emission has severe impact on human health and the ecological environment and effective monitoring of NO2 requires the detection limit (limit of detection) of several parts-per-billion (ppb). All organic semiconductor-based NO2 sensors fail to reach such a level. In this work, using an ion-in-conjugation inspired-polymer (poly(3,3'-diaminobenzidine-squarine, noted as PDBS) as the sensory material, NO2 can be detected as low as 1 ppb, which is the lowest among all reported organic NO2 sensors. In addition, the sensor has high sensitivity, good reversibility, and long-time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H-bonding and ion-dipole interaction to NO2 . The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion-in-conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H-bonding and ion-dipole attraction.

Platinum-Supported Zirconia Nanotube Arrays Supported on Graphene Aerogels Modified with Metal-Organic Frameworks: Adsorption and Oxidation of Formaldehyde at Room Temperature.

Precious-metal catalysts (e.g., Au, Rh, Ag, Ru, Pt, and Pd) supported on transition-metal oxides (e.g., Al2 O3 , Fe2 O3 , CeO2 , ZrO2 , Co3 O4 , MnO2 , TiO2 , and NiO) can effectively oxidize volatile organic compounds. In this study, porous platinum-supported zirconia materials have been prepared by a "surface-casting" method. The synthesized catalysts present an ordered nanotube structure and exhibited excellent performance toward the catalytic oxidation of formaldehyde. A facile method, utilizing a boiling water bath, was used to fabricate graphene aerogel (GA), and the macroscopic 3D Pt/ZrO2 -GA was modified by introducing an adjustable MOF coating by a surface step-by-step method. The unblocked mesoporous structure of the graphene aerogel facilitates the ingress and egress of reactants and product molecules. The selected 7 wt.% Pt/ZrO2 -GA-MOF-5 composite demonstrated excellent performance for HCHO adsorption. Additionally, this catalyst achieved around 90 % conversion when subjected to a reaction temperature of 70 °C (T90 % =70 °C). The Pt/ZrO2 -GA-MOF-5 composite induces a catalytic cycle, increasing the conversion by simultaneously adsorbing and oxidizing HCHO. This work provides a simple approach to increasing reactant concentration on the catalyst to increase the rate of reaction.