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The utilization of CO2 from flue gas as a C1 feedstock for the catalytic synthesis of high-valued oxazolidinones is highly important but challenging due to the low CO2 concentration and high activation barrier for CO2. Herein, we present an efficient and stable CuI-anchored porous covalent organic framework CuI@TpBD-COF for effective catalysis of the carboxylic cyclization reaction between propargylic amines and CO2 to produce various functionalized oxazolidinone derivatives under mild conditions. The yield is up to 99% and the turnover frequency (TOF) reaches a record value of 1058 h−1, significantly surpassing almost all previously reported metal heterogeneous catalysts. Furthermore, CuI@TpBD-COF also demonstrates efficient catalytic activity when simulated flue gas is used as the source of CO2. This work provides new guidance for the design of more efficient and eco-friendly noble-metal-free catalytic materials to drive the ideal CO2 chemical fixation process. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hybrid materials with photothermal conversion performance were prepared for low-energy desorption of NH 3. • Temperature of rGO@MOF-303(Al)-8% could be raised to about 75 °C in 10 min. • About 68% of NH 3 could be effectively desorbed from the adsorbent in 2-hour irradiation. • Excellent desorption performance of NH 3 under sunlight irradiation is attributed to the rapid temperature rise of the adsorbent. The capture, storage and release of NH 3 play a pivotal role in sustainable energy applications. However, to simultaneously achieve high adsorption capacity and low energy desorption remains a challenge. In this work, a novel class of hybrid materials with photothermal conversion performance have been developed by doping redox graphene and metal–organic framework of MOF-303(Al). It is found that the optimized rGO@MOF-303(Al)-8% exhibits high NH 3 uptake (17.0 mmol g−1) at 25.0 °C and 1.0 bar and exceptional photothermal conversion performance. Under the irradiation of simulated sunlight, its temperature can be raised to about 75 °C in 10 min. Even under direct natural sunlight irradiation, a stable equilibrium temperature of 53 °C may be achieved. Based on this excellent photothermal conversion performance, we investigated the desorption behavior of ammonia under visible light irradiation for the first time. We found that due to the breakdown of hydrogen bonds of NH 3 and N-N, N–H sites of rGO@MOF-303(Al)-8% caused by the rapid rise of temperature, approximately 68% of NH 3 could be effectively desorbed in 2-hour irradiation under ambient conditions. In addition, the optimized adsorbent demonstrated remarkable cycling stability. After undergoing 10 cycles, high adsorption capacity and efficient light-induced desorption of NH 3 were still maintained Thus, the present study provides a novel concept for high-capacity adsorption and low-energy desorption of NH 3 and other industrial gases. [ABSTRACT FROM AUTHOR]

The concerted catalysis throughout multiple elementary steps is key to impel sluggish hydrogen evolution reaction (HER). Herein, NiMo/Mo 2 N/NC(500-R) array is constructed by embedding densely packed NiMo/Mo 2 N heterojunctions into nanorod skeleton of nitrogen-rich derived carbons (NC), then followed by electrochemical surface reconstruction. The great electrochemical surface area of resultant electrocatalyst implies fully-exposed concerted diatomic-ensembles. The ensemble effect of unique heteronanojunction induces charge polarizations between Mo and Ni species, gives pseudocapacitance comparable to supercapacitors, and pumps mass transfers to refresh entire HER process. The exceptional activity is demonstrated by ultra-low overpotentials of 5.8 and 200.6 mV respectively at 10 and 1000 mA cm−2, the impressive durability is indicated by lasting alkaline HER for 1000 h at 1 A cm−2. Moreover, the performances in water-alkali electrolyzer outperform most reported catalysts. This work presents valuable insights into concerted catalysis and designing efficient and durable electrocatalysts by ensemble effect from different metal heterojunctions for commercial applications. [Display omitted] • Well-separated heteronanojunctions impart the enhanced intrinsic activity to array. • Ensemble effect refreshes the concerted diatomic sites by charge polarizations. • Electrocatalyst delivers ultra-low overpotentials in alkaline hydrogen evolution. • Striking durability makes electrocatalyst commercializable in hydrogen production. • In-depth insights offer guidance to design efficient and durable electrocatalysts. [ABSTRACT FROM AUTHOR]

Pd/C-[BMIm][BF 4 ] catalyst displayed high activity for acceptorless dehydrogenation of biomass-derived alcohols to produce aromatic ketones under mild conditions without any acid/base additives, and this catalyst could be recovered and reused for 5 runs without obvious activity loss. This work provides a potential approach for the effective utilization of renewable biomass resources to produce aromatic compounds and clean H 2. [Display omitted] • The combination of Pd/C with specific ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF 4 ]) displayed high activity for the dehydrogenation of aromatic alcohols to produce aromatic ketones. • The Pd/C-[BMIm][BF 4 ] pair promoted the dehydrogenation of aromatic alcohols and inhabited the hydrogenation of aromatic alcohols. • The catalyst could be recycled for 5 runs without obvious loss of activity. • Pd/C could be anchored and stabilized by the IL through interacting with [BMIm]+ cation, and both the [BMIm]+ cation and the [BF 4 ]- anion play vital roles in activating hydroxyl-H and hydroxyl α-H of the aromatic alcohol. Acceptorless dehydrogenation of alcohols is a promising pathway for biomass resource utilization and hydrogen supply, but still lacking for simple and effective catalysts. Herein, we report a metal-ionic liquids (ILs) catalyst for synergistical catalytic dehydrogenation of aromatic alcohols to aromatic ketones under mild conditions without any acid/base additives. It is found that the combination of Pd/C with 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF 4 ]) displays high activity for the dehydrogenation of biomass-derived alcohols including 1-phenyl-1-ethanol, 1-phenyl-1-propanol and 1-(4-methoxyphenyl)ethanol. Mechanistic studies reveal that the Pd/C can be anchored and stabilized by the IL via interacting with [BMIm]+ cation, and the [BF 4 ]- anion plays vital role in the activation of hydroxyl-H and α-H protons via hydrogen bonding interactions. These interactions create an effective microenvironmental for Pd/C catalyzing the cleavage of the hydroxyl-H and α-C H bonds of α-hydroxyl aromatic alcohols to generate aromatic ketones and H 2. Moreover, the Pd/C-[BMIm][BF 4 ] catalyst could be recovered and reused for 5 runs without obvious activity loss. This strategy provides more evidences for the synergetic catalysis of metal and ionic liquids and exhibits potential application prospects for hydrogen supply from renewable biomass-derived alcohols. [ABSTRACT FROM AUTHOR]