On-Demand, Highly Tunable, and Selective 5-Hydroxymethylfurfural Hydrogenation to Furan Diols Enabled by Ni and Ni₃Ga Alloy Catalysts

Abstract

Catalytic conversion of the biobased platform chemical 5hydroxymethylfurfural (HMF) into high-value-added products (e.g., diols) has attracted considerable attention, where controlling the products' selectivity is a crucial and challenging issue. Herein, a series of hydrotalcite-based Ni and Ni 3 Ga alloy catalysts were prepared for HMF hydrogenation into furan diols. By optimizing the loaded metal and reduction temperature, >99% BHMTHF and 95.6% BHMF yields were gained over Ni 1.5 Al-LDO-700 and Ni 1.5 GaAl-LDO-700, respectively, under mild conditions. Characterizations and DFT calculations showed that the doped Ga resulted in charge transfer from Ga to Ni and disrupted the Ni arrangement, which weakened the furan ring adsorption and favored its tilted adsorption on the Ni 3 Ga alloy, consequently inhibited deep hydrogenation, and selectively produced BHMF. These catalysts were also versatile for hydrogenation of other furan aldehydes, achieving high selectivity toward un-/saturated alcohols on demand. This study provides an advanced strategy for the rational design of superior catalysts for tuning product selectivity on demand, with practical potential for upgrading biomass-derived platform molecules.

Catalyst characteristics of the composite catalyst of Ru–Sn and Pd for hydrogenation of terephthalic acid

“…It can be seen that in the absence of any loaded metals, only raw materials and blank carriers are added, resulting in no production of target products. When additional metals such as Cu, Ni, Pd, and other third metals were loaded on the Ru–Sn catalyst, 15 respectively, the conversion rate of PTA exceeded 95%, while the yield of CHDM depended on the metal composition of the catalyst. The results indicate the addition of a Pd catalyst exhibited the best performance.…”

Mechanistic Insights into Hydrodeoxygenation of Lignin Derivatives over Ni Single Atoms Supported on Mo2C

“…5 Recent research on the mechanism of HDO has focused primarily on model compounds, where the reaction pathways of the model compounds and the correlations between catalyst structure and HDO performance of model compounds have been examined. 6,7 Due to their structure comprising both a phenolic hydroxyl (C aryl −OH) and an ether bond (C aryl −OCH 3 ), lignin-derived phenols such as guaiacol and dihydroeugenol (DHE) have attracted considerable study. 8−10 In recent years, the major trend for catalysts for HDO of lignin derivatives has been the use of precious metals and transition metals supported on various supports.…”

“…In recent years, the major trend for catalysts for HDO of lignin derivatives has been the use of precious metals and transition metals supported on various supports. ,− The majority of precious metal catalysts consist of palladium, ,− platinum, − rhodium, and ruthenium. − Nevertheless, taking into account the expense of precious metal catalysts, as inexpensive metals, transition metal catalysts have emerged as promising HDO catalysts. The transition metal sulfide catalysts, such as the NiMo sulfides and CoMo sulfides, show good activity for the hydrodeoxygenation of lignin-derived phenols. − However, these transition metal sulfide catalysts are rapidly deactivated and may contaminate the product with sulfur.…”

“…HDO can remove the oxygen content, saturate the most aromatic and alkene components, and subsequently increase the caloric value of bio-oil by boosting the H/C ratios in organic compounds . Recent research on the mechanism of HDO has focused primarily on model compounds, where the reaction pathways of the model compounds and the correlations between catalyst structure and HDO performance of model compounds have been examined. , Due to their structure comprising both a phenolic hydroxyl (C aryl –OH) and an ether bond (C aryl –OCH 3 ), lignin-derived phenols such as guaiacol and dihydroeugenol (DHE) have attracted considerable study. − …”

Selectivity-controllable hydrogen transfer reduction of α,β-unsaturated aldehydes over high-entropy catalysts

“…[15][16][17][18] Also, the modification of solid catalysts by means of alloying or selective poisoning can modulate the product selectivity of hydrogenation of unsaturated compounds. 19 It is found that, in the hydrogen transfer reaction of 5-hydroxymethyl furfural, noble metals such as Pd, Ru, and Rh preferentially undergo furan ring saturation to generate tetrahydrofuran-based products. However, when the noble metal catalysts are deactivated by sulfur poisoning, they can only hydrogenate the CO double bond to produce dimethylfuran.…”