Defining Pt-compressed CO₂synergy for selectivity control of furfural hydrogenation

Abstract

The development of a sustainable methodology for catalytic transformation of biomass-derived compounds to value-added chemicals is highly challenging. Most of the transitions are dominated by the use of additives, complicated reaction steps and large volumes of organic solvents. Compared to traditional organic solvents, alternative reaction media, which could be an ideal candidate for a viable extension of biomass-related reactions are rarely explored. Here, we elucidate a selective and efficient transformation of a biomass-derived aldehyde (furfural) to the corresponding alcohol, promoted in compressed CO 2 using a Pt/Al 2 O 3 catalyst. Furfural contains a furan ring with C]C and an aldehyde group, and is extremely reactive in a hydrogen atmosphere, resulting in several by-products and a threat to alcohol selectivity as well as catalyst life. The process described has a very high reaction rate (6000 h À1 ) with an excellent selectivity/yield (99%) of alcohol, without any organic solvents or metal additives.This strategy has several key features over existing methodologies, such as reduced waste, and facile product separation and purification (reduced energy consumption). Combining the throughput of experimental observation and molecular dynamics simulation, indeed the high diffusivity of compressed CO 2 controls the mobility of the compound, and eventually maintains the activity of the catalyst. Results are also compared for different solvents and solvent-less conditions. In particular, combination of an effective Pt catalyst with compressed CO 2 provides an encouraging alternative solution for upgradation of biomass related platform molecules.

Production of levulinic acid and alkyl levulinates: a process insight

“…[154][155][156] and noble metals (Ru, Pt, Pd, etc.) [157][158][159] based catalysts. High furfuryl alcohol yield and selectivity (up to 99 %) can be achieved by the control and the fine-tuning of reaction conditions: temperature, high or mild temperature condition depending on the catalyst; H2 pressure, typically high for deeper hydrogenation; time, longer times lead to higher hydrogenation yields; solvents and catalyst, mono-metallic or synergistically coupled with a second metal or specific support.…”

Recent Advances in Catalytic Hydrogenation of Furfural

“…As an example, the use of Pt/SO4-ZrO2 catalyst gave rise to 47% of MF and 33% of furan as the main products at a temperature of 240 °C ( Table 5, entry 2). Interestingly, the research of Chatterjee et al suggested that the formation of THFA could hamperthe catalyst robustness [176]. It was, as As an example, the use of Pt/SO 4 -ZrO 2 catalyst gave rise to 47% of MF and 33% of furan as the main products at a temperature of 240 • C ( Table 5, entry 2).…”

“…It was, as As an example, the use of Pt/SO 4 -ZrO 2 catalyst gave rise to 47% of MF and 33% of furan as the main products at a temperature of 240 • C ( Table 5, entry 2). Interestingly, the research of Chatterjee et al suggested that the formation of THFA could hamperthe catalyst robustness [176]. It was, as well, demonstrated that compressed CO 2 could have a synergy effect with Pt based catalyst and it could hinder the generation of THFA.…”

“…One of the methods for improving the catalytic performance, depending on the employed supports, is by modifying their surfaces with different functionalities. For instance Castelbou et al developed a new methodology for the synthesis of well-defined Pt nanoparticles that were supported on phosphine-functionalized silica [176]. The catalytic performance of the obtained material significantly improved ( Table 5, entry 7).…”

“…The catalytic performance of the obtained material significantly improved ( Table 5, entry 7). Modified carbon materials also showed an improvement on furfural selective hydrogenation [49,176]. For example, Liu et al prepared porous heteroatom-doped carbon materials, as supports for Pt nanoparticles.…”