Pt2CeO2 Heterojunction Supported on Multiwalled Carbon Nanotubes for Robust Electrocatalytic Oxidation of Methanol.

Herein, we prepared Pt2CeO2 heterojunction nanocluster (HJNS) on multiwalled carbon nanotubes (MWCNTs) in deep eutectic solvents (DESs) which is a special class of ionic liquids. The catalyst was then heat-treated at 400 °C in N2 (refer to Pt2CeO2/CNTs-400). The Pt2CeO2/CNTs-400 catalyst showed remarkably improved electrocatalytic performance towards methanol oxidation reaction (MOR) (839.1 mA mgPt-1) compared to Pt2CeO2/CNTs-500 (620.3 mA mgPt-1), Pt2CeO2/CNTs-300 (459.2 mA mgPt-1), Pt2CeO2/CNTs (641.6 mAmg-1) (the catalyst which has not been heat-treated) and commercial Pt/C (229.9 mAmg-1). Additionally, the Pt2CeO2/CNTs-400 catalyst also showed better CO poisoning resistance (onset potential: 0.47 V) compared to Pt2CeO2/CNTs (0.56 V) and commercial Pt/C (0.58 V). The improved performance of Pt2CeO2/CNTs-400 catalyst is attributed to the addition of appropriate CeO2, which changed the electronic state around the Pt atoms, lowered the d-band of Pt atoms, formed more Ce-O-Pt bonds acting as new active sites, affected the adsorption of toxic intermediates and weakened the dissolution of Pt; on the other hand, with the assistance of thermal treatment at 400 °C, the obtained Pt2CeO2 HJNS expose more new active sites at the interface between Pt and CeO2 to enhance the electrochemical active surface area (ECSA) and the dehydrogenation process of MOR. Thirdly, DES is beneficial to the increase of the effective component Pt(0) in the carbonization process. The study shows a new way to construct high-performance Pt-CeO2 catalyst for the direct methanol fuel cell (DMFC).

A "Special" Solvent to Prepare Alloyed Pd2Ni1 Nanoclusters on a MWCNT Catalyst for Enhanced Electrocatalytic Oxidation of Formic Acid.

Herein, an electrocatalyst with Pd2Ni1 nanoclusters, supporting multiwalled carbon nanotubes (MWCNTs) (referred to Pd2Ni1/CNTs), was fabricated with deep eutectic solvents (DES), which simultaneously served as reducing agent, dispersant, and solvent. The mass activity of the catalyst for formic acid oxidation reaction (FAOR) was increased nearly four times compared to a Pd/C catalyst. The excellent catalytic activity of Pd2Ni1/CNTs was ascribed to the special nanocluster structure and appropriate Ni doping, which changed the electron configuration of Pd to reduce the d-band and to produce a Pd-Ni bond as a new active sites. These newly added Ni sites obtained more OH- to release more effective active sites by interacting with the intermediate produced in the first step of FAOR. Hence, this study provides a new method for preparing a Pd-Ni catalyst with high catalytic performance.

Dimension Engineering in Noble-Metal-Based Electrocatalysts for Water Splitting.

Dimension engineering plays a critical role in determining the electrocatalytic performance of catalysts towards water electrolysis since it is highly sensitive to the surface and interface properties. Bearing these considerations into mind, intensive efforts have been devoted to the rational dimension design and engineering, and many advanced nanocatalysts with multidimensions have been successfully fabricated. Aiming to provide more guidance for the fabrication of highly efficient noble-metal-based electrocatalysts, this review has focused on the recent progress in dimension engineering of noble-metal-based electrocatalysts towards water splitting, including the advanced engineering strategies, the application of noble-metal-based electrocatalysts with distinctive geometric structure from 0D to 1D, 2D, 3D, and multidimensions. In addition, the perspective insights and challenges of the dimension engineering in the noble-metal-based electrocatalysts is also systematically discussed.

Pd3Co1 Alloy Nanocluster on the MWCNT Catalyst for Efficient Formic Acid Electro-Oxidation.

In this study, the Pd3Co1 alloy nanocluster from a multiwalled carbon nanotube (MWCTN) catalyst was fabricated in deep eutectic solvents (DESs) (referred to Pd3Co1/CNTs). The catalyst shows a better mass activity towards the formic acid oxidation reaction (FAOR) (2410.1 mA mgPd-1), a better anti-CO toxicity (0.36 V) than Pd/CNTs and commercial Pd/C. The improved performance of Pd3Co1/CNTs is attributed to appropriate Co doping, which changed the electronic state around the Pd atom, lowered the d-band of Pd, formed a new Pd-Co bond act at the active sites, affected the adsorption of the toxic intermediates and weakened the dissolution of Pd; moreover, with the assistance of DES, the obtained ultrafine Pd3Co1 nanoalloy exposes more active sites to enhance the dehydrogenation process of the FAOR. The study shows a new way to construct a high-performance Pd-alloy catalyst for the direct formic acid fuel cell.

Visible-light-promoted decarboxylative radical cascade cyclization to acylated benzimidazo/indolo[2,1-a]isoquinolin-6(5H)-ones in water.

A metal-free visible-light-induced decarboxylative radical addition/cyclization procedure at room temperature was described for the synthesis of acylated benzimidazo/indolo[2,1-a]isoquinolines. The procedure was prepared in water via a reaction of functionalized 2-arylbenzoimidazoles or 2,3-diarylindoles and α-oxocarboxylic acids in the presence of phenyliodine(iii) diacetate (PIDA) in one step under mild reaction conditions. In this procedure, traditional heating and metal reagents could be effectively avoided to access 1,4-dicarbonyl-containing benzimidazo/indolo[2,1-a]isoquinoline-6(5H)-ones in satisfactory yields.

Recent advances in acyl radical enabled reactions between aldehydes and alkenes.

Radical-mediated functionalization of alkenes has been emerging as an elegant and straightforward protocol to increase molecule complexity. Moreover, the abstraction of a hydrogen atom from aldehydes to afford acyl radicals has evolved as a rising star due to its high atom-economy and the ready availability of aldehydes. Considering the great influence and synthetic potential of acyl radical enabled reactions between aldehydes and alkenes, we provide a summary of the state of the art in this field with a specific emphasis on the working models and corresponding mechanisms. The discussion is divided according to the kind of alkenes and reaction type.

Palladium supported on triazolyl-functionalized hypercrosslinked polymers as a recyclable catalyst for Suzuki-Miyaura coupling reactions.

A novel hypercrosslinked polymers-palladium (HCPs-Pd) catalyst was successfully prepared via the external cross-linking reactions of substituted 1,2,3-triazoles with benzene and formaldehyde dimethyl acetal. The preparation of HCPs-Pd has the advantages of low cost, mild conditions, simple procedure, easy separation and high yield. The catalyst structure and composition were characterized by N2 sorption, TGA, FT-IR, SEM, EDX, TEM, XPS and ICP-AES. The HCPs were found to possess high specific surface area, large micropore volume, chemical and thermal stability, low skeletal bone density and good dispersion for palladium chloride. The catalytic performance of HCPs-Pd was evaluated in Suzuki-Miyaura coupling reactions. The results show that HCPs-Pd is a highly active catalyst for the Suzuki-Miyaura coupling reaction in H2O/EtOH solvent with TON numbers up to 1.66 × 104. The yield of biaryls reached 99%. In this reaction, the catalyst was easily recovered and reused six times without a significant decrease in activity.

Palladium catalyst immobilized on functionalized microporous organic polymers for C-C coupling reactions.

Two microporous organic polymer immobilized palladium (MOP-Pd) catalysts were prepared from benzene and 1,10-phenanthroline by Scholl coupling reaction and Friedel-Crafts reaction, respectively. The structure and composition of the catalyst were characterized by FT-IR, TGA, N2 sorption, SEM, TEM, ICP-AES and XPS. MOP-Pd catalysts were found to possess high specific surface areas, large pore volume and low skeletal bone density. Moreover, the immobilized catalyst also had advantages, such as readily available raw materials, chemical and thermal stability, and low synthetic cost. The Pd catalyst is an effective heterogeneous catalyst for carbon-carbon (C-C) coupling reactions, such as the Heck reaction and Suzuki-Miyaura reaction, affording good to high yields. In these reactions, the catalyst was easily recovered and reused five times without significant activity loss.

Hypervalent iodine-triggered transformation of homopropargyl sulfonamides into dihalo-2,3-dihydropyrroles.

A novel hypervalent iodine-triggered hydroamination of homopropargyl sulfonamides with copper halides to obtain dihalo-2,3-dihydropyrroles was efficiently developed. The reaction can provide access to chloro/bromo-cyclization extended from iodocyclization to prepare potentially useful halogenated building blocks for drug development with broad functional group tolerance and high yield yet in a short time.