Layered Double Hydroxide‐Derived Bimetallic Ni−Cu Catalysts Prompted the Efficient Conversion of γ‐Valerolactone to 2‐Methyltetrahydrofuran

Abstract

The catalytic upgrading of γ‐valerolactone (GVL) to liquid biofuel, which is of great importance to the development of new types of high‐performance heterogeneous catalysts, is regarded as a technically difficult task because of the thermal stability of GVL. Consequently, in this study, a series of nanocatalysts NixCu3‐x/Al2O3 (x=0, 1, 1.5, 2, and 3) derived from layered double hydroxide (LDH) precursors were prepared for the hydrogenation of biomass‐derived GVL to 2‐methyltetrahydrofuran (2‐MTHF). The optimal bimetallic Ni2Cu1/Al2O3 catalyst showed high 2‐MTHF selectivity with complete GVL conversion. Detailed characterization revealed cooperation between the acid sites and Ni−Cu alloy in the bimetallic catalysts, which was responsible for their high activities. More importantly, the strong interaction between Ni and Cu changed the surface chemical environment, which generated different copper species and enhanced the H2 activation ability. The reusability of the Ni2Cu1/Al2O3 catalyst and the effect of the reaction conditions, such as temperature, H2 pressure, and solvent, were also investigated.

One-pot selective hydroconversion of levulinic acid to 2-methyltetrahydrofuran catalyzed by Ni-based catalysts derived from phyllosilicates

“…As illustrated in Scheme 1, the hydrogenation of GVL can proceed via various routes and lead to the formation of different products depending on the kinds of active sites on the catalyst surface. The metal active sites along with Brønsted sites favor the cleavage of the C–O bond on the methyl side of GVL and result in the formation of VA. 10,30,32 In contrast, the metal active sites coordinated with Lewis acid sites will enhance the formation of 1,4-PDO. 3,33 The formed 1,4-PDO will be further cyclodehydrated over acid sites to produce 2-MTHF.…”

“…For the consecutive conversion of LA into 2-MTHF, the selective ring-opening reaction of the GVL intermediate is the ratedetermining step for the chemical stability of GVL. 30,31 Hence, we rst examined the catalytic performance of the various catalysts for the hydrogenation of GVL. The catalytic reactions of the GVL hydrogenation were assessed at 220 C and 5 MPa H 2 with 2-butanol as a solvent for 5 h. The obtained reaction results are listed in Table 2.…”

Catalytic hydrodeoxygenation of neat levulinic acid into 2-methyltetrahydrofuran using a cobalt phosphine complex and Sc(OTf)3co-catalytic system

“…Arias et al 17 and Obregón et al 18 developed a Ni–Cu alloy catalyst Ni–Cu/Al 2 O 3 , and in addition to hydrogen, isopropanol and 2-butanol were used as hydrogen sources for the transfer hydrogenation, respectively, and medium yields of 2-MeTHF were obtained. Lu and Ji et al 19 prepared a Ni 2 Cu 1 /Al 2 O 3 catalyst derived from layered double hydroxides, which markedly enhanced the catalytic performance and afforded an 88.1% yield of 2-MeTHF. Other metal-doped nickel catalysts can also catalyze the hydrodeoxygenation of GVL.…”

Alloy‐Driven Efficient Electrocatalytic Oxidation of Biomass‐Derived 5‐Hydroxymethylfurfural towards 2,5‐Furandicarboxylic Acid: A Review

“…In 2015, the United Nations set the sustainable development goals (SDGs) to be achieved by 2030, in which developing affordable and clean energy was emphasized as one of the worldwide core concerns; thus, adequately exploring renewable resources to construct a sustainable energy system has been ushered into a new era [2] . As one of the environmentally friendly energy resources, biomass energy is the energy stored in biomass feedstocks by solar energy in the form of chemical energy [3] . Biomass resources are the only large‐scale non‐fossil carbon source that can be processed into high value‐added liquefied chemicals, [4] and therefore strengthening the utilization of biomass resources is of great significance for cultivating a greener modern lifestyle [5] .…”

“…[2] As one of the environmentally friendly energy resources, biomass energy is the energy stored in biomass feedstocks by solar energy in the form of chemical energy. [3] Biomass resources are the only large-scale non-fossil carbon source that can be processed into high value-added liquefied chemicals, [4] and therefore strengthening the utilization of biomass resources is of great significance for cultivating a greener modern lifestyle. [5] For this reason, the concept of biorefinery technology was proposed, [6] which refers to the continuous production of value-added chemicals and biofuels from biomass feedstocks.…”