Biomass-Derived Platform Chemicals: Thermodynamic Studies on the Conversion of 5-Hydroxymethylfurfural into Bulk Intermediates

Abstract

This work was undertaken to obtain new thermochemical data for 5-hydroxymethylfurfural (HMF) and parent compounds. The standard molar enthalpy of formation in the gaseous state of HMF was obtained from combustion calorimetry, differential scanning calorimetry (DSC), and measurements of the temperature dependence of the vapor pressure by the transpiration method. To verify the experimental data, ab initio calculations of all compounds were performed. Enthalpies of formation derived from the G3MP2 method are in an excellent agreement with the experimental results. A weak hydrogen bond in HMF was revealed using ab initio methods. Thermodynamic analysis of the transformation of HMF to the bulk intermediates according to hydrogenation and oxidation pathways has revealed a very high feasibility of these reactions, with equilibrium constants that are completely shifted to the desired reaction products even at 298 K.

Electrocatalytic Hydrogenation of 5‐Hydroxymethylfurfural in Acidic Solution

“…Based on the above observations, we now discusst he possible mechanistic implications for the electrocatalytic hydrogenation of HMF.A sr eported in our previous work, [15] the equilibrium potentialo fH MF hydrogenation to DHMF is around0 .1 V (vs. RHE), based on the Gibbs free energy changes in the gas phase at 298 K, [17] and therefore we conclude that, in neutral conditions, the identicalo nset potentials (À0.5 AE 0.2 V) on all conductive catalysts suggestt he absence of as trongc atalytic effect. However,u nder acidic conditions as studied here, the onset potentials for HMFh ydrogenation are shifted to more positive potentials, ranging À0.4 to 0V RHE on transition d metals and À0.7 to À0.25 V RHE on post-transition sp metals as summarized in Figure 3.…”

Processed Lignin as a Byproduct of the Generation of 5‐(Chloromethyl)furfural from Biomass: A Promising New Mesoporous Material

“…Mesoporosity may thusa lso be an advantage in the productiono fn ew adsorbent materials [13] or catalystsupports. [15] CMF is acarbohydrate-derived platform molecule of value to gain accesst o ar ange of renewable chemical and materials markets and is rapidly advancinga sa na lternative to HMF (2) [16] because of its greater accessibility from raw biomass. [15] CMF is acarbohydrate-derived platform molecule of value to gain accesst o ar ange of renewable chemical and materials markets and is rapidly advancinga sa na lternative to HMF (2) [16] because of its greater accessibility from raw biomass.…”

“…[14] The lignin used for this study was aby-product of the biphasic acid/solvent reactionu sed to produce 5-(chloromethyl)furfural (CMF; 1; Figure 1) from lignocellulose. [15] CMF is acarbohydrate-derived platform molecule of value to gain accesst o ar ange of renewable chemical and materials markets and is rapidly advancinga sa na lternative to HMF (2) [16] because of its greater accessibility from raw biomass.…”

Treatment of Biomass with Supercritical Water

“…Diese Substanz ist nach chemischer Umwandlung zur Dicarbonsäure, Diamin, Diol etc. eine interessante biogene Ausgangssubstanz für Polymere [31]. Die oben erwähnte Polymerisation unter hydrothermalen Bedingungen ist die Hauptreaktion bei der hydrothermalen Karbonisierung von Biomasse.…”