Dehydrogenation of formic acid over various Ru‐arene complexes containing N‐donor chelating ligands was investigated in H2O and isolated and characterized several important catalytic intermediate species to elucidate the reaction pathway for formic acid dehydrogenation. Among the studied complexes, Ru‐arene complexes, namely [(η6‐C6H6)Ru(κ2‐NpyNH2‐AmQ)Cl]+ (C‐2), [(η6‐C10H14)Ru(κ2‐NpyNH2‐AmQ)Cl]+ (C‐3) and [(η6‐C6H6)Ru(κ2‐NpyNHMe‐MAmQ)Cl]+ (C‐4) [AmQ = 8‐aminoquinoline and MAmQ = 8‐(N‐methylamino)quinoline] were proved to be the efficient catalysts for formic acid dehydrogenation at 90 °C, even in the absence of base. With an initial TOF of 940 h–1, complex C‐4 displayed the highest catalytic activity for formic acid dehydrogenation in H2O and it can be recycled up to 5 times with a TON of 2248. Effect of temperature, pH, formic acid and catalyst concentration on the reaction kinetics were also investigated in detail. Extensive mechanistic investigations using mass spectrometry and NMR evidenced the formation of a coordinatively unsaturated species [(η6‐C6H6)Ru(κ2‐NpyNH‐AmQ)]+ (C‐2A)/[(η6‐C6H6)Ru(κ2‐NpyNMe‐MAmQ)]+ (C‐4A) as the active component during the catalytic dehydrogenation of formic acid. We further characterized the dimer‐form of C‐2A, possibly the catalyst resting state, by single‐crystal X‐ray crystallography.

Traditionally, methanol reforming at very high temperature > 200 ℃ has been explored for hydrogen production. Here, we show that in situ generated ruthenium nanoparticles (ca. 1.5 nm) from an...

To understand critical problems associated with solid waste and its consequences for the environment, a laboratory experiment is presented on the synthesis of aluminum-based metal−organic framework (MOF) MIL-53(Al) from household waste (PET bottles and aluminum foil/can), for undergraduate students of chemistry. This work is designed to teach students the research methodology and basic understanding of MOFs and their application in carbon capture and storage (CCS). Students also learnt several instrumentation techniques such as UV−vis spectroscopy, powder X-ray diffraction (P-XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and gas sorption to characterize the physicochemical properties of . The facile production of MIL-53(Al) enabled the students to investigate its applicability in CO 2 sorption. The calculations of essential parameters such as CO 2 over N 2 selectivity and the use of statistical tools in data processing are also explained to the students. In the end, the instructor presented his/her feedback by evaluating the answer sheets (pre-and postlab work) and by demonstrating the overall lab work through a model presentation.

We synthesized pyridylamine ligated arene-Ru(II) complexes and employed these complexes for the catalytic acceptorless dehydrogenation of primary alcohols to carboxylic acids. All the synthesized complexes [Ru]-1−[Ru]-10 are characterized using several spectro-analytical techniques, and the structures of complexes [Ru]-1, [Ru]-2, and [Ru]-5 are determined using single crystal X-ray crystallography. Efficient catalytic conversion of primary alcohols to potassium carboxylates or carboxylic acids is achieved in toluene with the quantitative release of hydrogen gas. The studied protocol for carboxylic acid synthesis with hydrogen generation is also employed for a wide range of substrates, including aliphatic alcohols, aromatic alcohols, and heteroaromatic alcohols, to obtain respective carboxylic acids in good yields (up to 86%). The studied arene-Ru catalysts also exhibit superior catalytic activity for the bulk reaction to achieve a turnover number of 1378. Moreover, extensive mass investigations are also performed to elucidate the mechanistic pathway by identifying the crucial catalytic intermediates, including aldehyde and diol coordinated Ru species under the catalytic and controlled reaction conditions.

Efficient hydrogen production from aqueous formaldehyde with appreciably high TOF and TON achieved over an in situ generated ruthenium catalyst in water at 95 °C.