Catalytic Activity of Ti‐based MXenes for the Hydrogenation of Furfural

Abstract

Herein we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. The bifunctional acidmetal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

Synthesis of new two‐dimensional titanium carbonitride Ti2C0.5N0.5TxMXene and its performance as an electrode material for sodium‐ion battery

“…The importance of the present new carbonitride MXene goes beyond SIBs. Since Ti 3 CNT x were found to outperform Ti 3 C 2 T x for many applications, such as electrodes for lithium and potassium ion batteries, 30,67 catalysis, 39 and electromagnetic interference shielding 40 . Therefore, it is reasonable to predict that Ti 2 C 0.5 N 0.5 T x will find its way to other applications beyond SIBs.…”

“…To date, over 40 different MXene compositions have been reported; the vast majority of these MXenes are carbides with only a few exceptions—several nitrides and only one carbonitride ( viz ., Ti 3 CNT x ) 27 . The latter has shown distinct properties and behavior compared with Ti 3 C 2 T x in many applications including energy storage, 28–33 optics, 34,35 catalysis, 36–39 electromagnetic shielding, 40,41 sensing, 42,43 and so forth. This distinct behavior of Ti 3 CNT x compared with Ti 3 C 2 T x provides a strong motivation to develop other new carbonitrides to join the MXene family.…”

Experimental and Computational Analysis of MnO2@V2C-MXene for Enhanced Energy Storage

“…MXenes are obtained from selective etching of ‘A’ layers from their lamellar precursors, known as MAX. MXenes are a huge class of ternary carbides and nitrides, including more than 70 reported phases until now, along with various solid solutions and ordered double transition metal structures [ 19 , 20 , 21 , 22 , 23 , 24 , 25 ].…”

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

“…Hf-TUD-1(x) catalysts are the first Hf-mesoporous silicates reported for Fur conversion using secROH. The catalytic results for Hf-TUD-1(x) were compared with literature data for fully inorganic heterogeneous non-noble metal catalysts tested for Fur conversion to AMFs in alcohol medium ( Table 2 ) [ 34 , 36 , 37 , 39 , 42 , 43 , 61 , 62 , 65 , 67 , 78 , 79 , 80 , 81 , 82 , 83 , 84 , 85 ]. The present work does not concern noble metal catalysts for Fur conversion, which may be found in a vast literature such as the following references, just to cite a few [ 86 , 87 , 88 ].…”