16873-17-9Relevant articles and documents
Introducing Water-Network-Assisted Proton Transfer for Boosted Electrocatalytic Hydrogen Evolution with Cobalt Corrole
Li, Xialiang,Lv, Bin,Zhang, Xue-Peng,Jin, Xiaotong,Guo, Kai,Zhou, Dexia,Bian, Hongtao,Zhang, Wei,Apfel, Ulf-Peter,Cao, Rui
supporting information, (2022/01/11)
Proton transfer is vital for many biological and chemical reactions. Hydrogen-bonded water-containing networks are often found in enzymes to assist proton transfer, but similar strategy has been rarely presented by synthetic catalysts. We herein report the Co corrole 1 with an appended crown ether unit and its boosted activity for the hydrogen evolution reaction (HER). Crystallographic and 1H NMR studies proved that the crown ether of 1 can grab water via hydrogen bonds. By using protic acids as proton sources, the HER activity of 1 was largely boosted with added water, while the activity of crown-ether-free analogues showed very small enhancement. Inhibition studies by adding 1) external 18-crown-6-ether to extract water molecules and 2) potassium ion or N-benzyl-n-butylamine to block the crown ether of 1 further confirmed its critical role in assisting proton transfer via grabbed water molecules. This work presents a synthetic example to boost HER through water-containing networks.
Bis-Imidazole Methane Ligated Ruthenium(II) Complexes: Synthesis, Characterization, and Catalytic Activity for Hydrogen Production from Formic Acid in Water
Deka, Hemanta,Patra, Soumyadip,Singh, Sanjay K.
supporting information, p. 14275 - 14285 (2021/10/05)
A series of half sandwich arene-ruthenium complexes [(η6-arene)RuCl(κ2-L)]+ ([Ru]-1-[Ru]-10) containing bis-imidazole methane-based ligands {4,4′-(phenylmethylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L1), {4,4′-((4-methoxyphenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L2), {4,4′-((2-methoxyphenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L3), {4,4′-((4-chlorophenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L4), and {4,4′-((2-chlorophenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L5) are synthesized. The synthesized and purified complexes ([Ru]-1-[Ru]-10) are further employed for hydrogen production from formic acid in aqueous medium. Among the investigated complexes, [(η6-p-cymene)RuCl(κ2-L2)]+ [Ru]-2, having Ru(II) coordinated 4-methoxy phenyl substituted bis-imidazole methane ligand (L2), outperformed over others, displaying a higher catalytic turnover of 8830 and high efficiency (TOF = 1545 h-1) with appreciably high long-term stability for formic acid dehydrogenation in water.
Acid- and Base-Catalyzed Hydrolytic Hydrogen Evolution from Diboronic Acid
Wang, Yi,Shen, Jialu,Huang, Yu,Liu, Xiang,Zhao, Qiuxia,Astruc, Didier
, p. 3013 - 3018 (2021/03/26)
The efficient production of H2 from hydrogen-rich sources, particularly from water, is a crucial task and a great challenge, both as a sustainable energy source and on the laboratory scale for hydrogenation reactions. Herein, a facile and effective synthesis of H2 and D2 from only acid- or base-catalyzed metal-free hydrolysis of B2(OH)4, a current borylation reagent, has been developed without any transition metal or ligand. Acid-catalyzed H2 evolution was completed in 4 min, whereas the base-catalyzed process needed 6 min. The large kinetic isotopic effects for this reaction with D2O, deuteration experiments and mechanistic studies have confirmed that both H atoms of H2 originate from water using either of these reactions. This new, metal-free catalytic system holds several advantages, such as high efficiency, simplicity of operation, sustainability, economy, and potential further use.