Synergistic N‐Heterocyclic Carbene/Palladium‐Catalyzed Umpolung 1,4‐Addition of Aryl Iodides to Enals

An umpolung 1,4‐addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β‐diaryl propanoate derivatives. This system is not only the first reported palladium‐catalyzed arylation of NHC‐bound homoenolates but also expands the scope of NHC‐induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture‐sensitive organometallic reagents.     

π‐Interactions between Cyclic Carbocations and Aromatics Cause Zeolite Deactivation in Methanol‐to‐Hydrocarbon Conversion

The understanding of catalyst deactivation represents one of the major challenges for the methanol‐to‐hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π‐interactions in catalyst deactivation in the MTH reaction on zeolites H‐SSZ‐13 and H‐ZSM‐5. π‐interaction‐induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two‐dimensional solid‐state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology.     

Enriched Surface Oxygen Vacancies of Photoanodes by Photoetching with Enhanced Charge Separation

A facile photoetching approach is described that alleviates the negative effects from bulk defects by confining the oxygen vacancy (O_vac) at the surface of BiVO₄ photoanode, by 10‐minute photoetching. This strategy could induce enriched O_vac at the surface of BiVO₄, which avoids the formation of excessive bulk defects. A mechanism is proposed to explain the enhanced charge separation at the BiVO₄ /electrolyte interface, which is supported by density functional theory (DFT) calculations. The optimized BiVO₄ with enriched surface O_vac presents the highest photocurrent among undoped BiVO₄ photoanodes. Upon loading FeOOH/NiOOH cocatalysts, photoetched BiVO₄ photoanode reaches a considerable water oxidation photocurrent of 3.0 mA cm^?2 at 0.6 V vs. reversible hydrogen electrode. An unbiased solar‐to‐hydrogen conversion efficiency of 3.5 % is realized by this BiVO₄ photoanode and a Si photocathode under 1 sun illumination.     

Photoinduced Single‐Electron Transfer as an Enabling Principle in the Radical Borylation of Alkenes with NHC–Borane

A photoinduced SET process enables the direct B?H bond activation of NHC–boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this photoinduced reaction simply takes advantage of the beneficial redox potentials of NHC–boranes, thus obviating the need for extra radical initiators. The resulting NHC–boryl radical was used for the borylation of a wide range of α‐trifluoromethylalkenes and alkenes with diverse electronic and structural features, providing facile access to highly functionalized borylated molecules. Labeling and photoquenching experiments provide insight into the mechanism of this photoinduced SET pathway.     

In situ Growth of a Cobalt‐based Metal‐organic Framework on Multi‐walled Carbon Nanotubes for Simultaneously Detection of Hydroquinone and Catechol.

In the present study, we report a facile method for preparing a porous MWCNTs/ZIF‐67 nanocomposite with the help of a morphology‐maintained ZIF‐67 in situ growth on multi‐walled carbon nanotubes. Interesting, the MWCNTs/ZIF‐67 nanocomposite demonstrated excellent electrochemical activity for hydroquinone (HQ) and catechol (CC) attribute to the effective interconnections ZIF‐67 crystals and MWCNTs. The analytical curves for HQ and CC obtained by differential pulse voltammetry (DPV) were linear in the range from 0.5 to 100 μM. Benefitting from the excellent conductivity of MWCNTs as well as the high surface area and porosity of ZIF‐67, the advanced nanocomposite displayed good reproducibility, high selectivity and excellent stability, and was successfully employed to assay the content of dihydroxybenzene isomers in the lake water samples.     

Synthesis of Zinc Tetraaminophthalocyanine Functionalized Graphene Nanosheets as an Enhanced Material for Sensitive Electrochemical Determination of Uric Acid

A new electrochemical sensor material has been fabricated via the non‐covalent functionalization of reduced graphene oxide (rGO) and soluble tetramino zincphthalocyanines (ZnPc‐NH₂). Immobilization of uricase onto the synthesized nanohybrids can evidently improve the electrocatalytic activity and selectivity. The obtained composite membrane possesses a great enhancement of electron transfer rate and excellent synergistic electrocatalytic effect toward uric acid (UA) oxidation under the working potential at 0.620 V vs. Ag/AgCl with a scan rate of 0.125 V/s. The effects of the experimental parameters on the electrochemical oxidation responses of UA were investigated and optimized in detail. Under the optimized conditions, the peak currents were proportional to the UA concentration in a range from 0.5 to 100 μmol/L with detection limit of 0.15 μmol/L. Moreover, the developed sensor was applied for UA determination in human urine samples with high accuracy and satisfactory recovery, which is envisioned to have promising applications in monitoring UA in clinical research.     

High‐Performance K–CO2 Batteries Based on Metal‐Free Carbon Electrocatalysts

Metal–CO₂ batteries have attracted much attention owing to their high energy density and use of greenhouse CO₂ waste as the energy source. However, the increasing cost of lithium and the low discharge potential of Na–CO₂ batteries create obstacles for practical applications of Li/Na–CO₂ batteries. Recently, earth‐abundant potassium ions have attracted considerable interest as fast ionic charge carriers for electrochemical energy storage. Herein, we report the first K–CO₂ battery with a carbon‐based metal‐free electrocatalyst. The battery shows a higher theoretical discharge potential (E^?=2.48 V) than that of Na–CO₂ batteries (E^?=2.35 V) and can operate for more than 250 cycles (1500 h) with a cutoff capacity of 300 mA h g^?1. Combined DFT calculations and experimental observations revealed a reaction mechanism involving the reversible formation and decomposition of P12₁/c1‐type K₂CO₃ at the efficient carbon‐based catalyst.     

Amorphous Metal–Organic Framework‐Dominated Nanocomposites with Both Compositional and Structural Heterogeneity for Oxygen Evolution

Amorphous metal–organic frameworks (aMOFs) are an emerging family of attractive materials with great application potential, however aMOFs are usually prepared under harsh conditions and aMOFs with complex compositions and structures are rarely reported. In this work, an aMOF‐dominated nanocomposite (aMOF‐NC) with both structural and compositional complexity has been synthesized using a facile approach. A ligand‐competition amorphization mechanism is proposed based on experimental and density functional theory calculation results. The aMOF‐NC possesses a core–shell nanorod@nanosheet architecture, including a Fe‐rich Fe‐Co‐aMOF core and a Co‐rich Fe‐Co‐aMOF shell in the core–shell structured nanorod, and amorphous Co(OH)₂ nanosheets as the outer layer. Benefiting from the structural and compositional heterogeneity, the aMOF‐NC demonstrates an excellent oxygen evolution reaction activity with a low overpotential of 249 mV at 10.0 mA cm^?2 and Tafel slope of 39.5 mV dec^?1.     

Enhanced Surface Interactions Enable Fast Li+ Conduction in Oxide/Polymer Composite Electrolyte

Li⁺‐conducting oxides are considered better ceramic fillers than Li⁺‐insulating oxides for improving Li⁺ conductivity in composite polymer electrolytes owing to their ability to conduct Li⁺ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li⁺‐insulating oxides (fluorite Gd_0.1Ce_0.9O_1.95 and perovskite La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.55) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li⁺ conductivity above 10^?4 S cm^?1 at 30 °C. Li solid‐state NMR results show an increase in Li⁺ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O^2? of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li⁺ transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.     

Gold(I)‐Catalyzed Cycloisomerization of 3‐Alkoxyl‐1,6‐diynes: A Facile Access to Bicyclo[2.2.1]hept‐5‐en‐2‐ones

A novel gold‐catalyzed cycloisomerization of 1,6‐diynes was achieved, providing an atom‐economic approach to a diverse set of bicyclo[2.2.1]hept‐5‐en‐2‐ones in moderate to good yields. With unsymmetrical starting materials with two different internal alkynyl substituents, to some extent, the regioselectivity could be controlled by both electronic and steric factors. This unprecedented reactivity pattern may inspire new and unconventional strategies for the preparation of bridged ring systems.