Surface engineering of earth-abundant Fe catalysts for selective hydrodeoxygenation of phenolics in liquid phase

Abstract

Tailoring the graphene-covered Fe with Cs modifies the surface electronic properties of the catalysts such that selective C–O bond cleavage of phenol is achieved in liquid phase by inhibiting the facile tautomerization followed by ring saturation.

Elucidating the Active Site and the Role of Alkali Metals in Selective Hydrodeoxygenation of Phenols over Iron‐Carbide‐based Catalyst

“…We further investigated the status of these alkali metals on Fe 3 C by temperature‐programmed decomposition (TPD) of catalysts after a pretreatment at 300 °C for 4 h to achieve the alkali metal doped G@Fe (Figure S13). All the alkali‐metal‐promoted catalysts exhibit the production of CO 2 starting from around 350 °C, which is likely derived from the decomposition of carbonate [18] . This is in line with the XPS result in Figure S6.…”

“…The above results unanimously revealed a Cs‐doped graphene‐covered Fe 0 active phase (i. e., Cs−G@Fe). However, the C 1 s XPS spectrum of spent Cs/Fe 3 C still cannot exclude the possible presence of carbidic carbon (binding energy≈283.3 eV [27] ) in the developed Cs−G@Fe as shown in Figure S7 and our previously reported catalyst [18] . To further verify the proposed Cs−G@Fe active site, we directly synthesized and investigated G@Fe catalysts containing no carbidic carbon.…”

“…Based on our previous work on HDO of phenolics, herein, we further explore the iron‐carbide‐based catalyst for the selective HDO of phenols. Given that Cs plays a pivotal role in promoting DDO selectivity on the G@Fe catalyst, [18] together with the variable capacity of electron donation by alkali metals, [19] effect of alkali metals are also explored on the iron‐carbide‐based catalysts. A suite of characterizations of the catalysts including high‐resolution transmission electron microscopy (HRTEM), X‐ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (EELS), and Raman spectroscopy, among others, revealed that the carbide rapidly reconstructed to a defective graphene covered metallic Fe.…”

MoOx-Decorated ZrO2 Nanostructures Supporting Ru Nanoclusters for Selective Hydrodeoxygenation of Anisole to Benzene

“…4 Currently, the catalytic hydrodeoxygenation (HDO) of oxygenates is regarded as an available and effective way to cope with these problems. 5,6 During the HDO process, the cleavage of C−O bonds usually goes through hydrogenation, hydrogenolysis, hydrocracking, dehydration, or decarboxylation under harsh conditions. 3,4,7,8 After the reaction, a series of aromatic and aliphatic derivates can be attained.…”

“…In recent years, the efficient upgrading of renewable biomass sources to produce various chemicals and bio-oils has attracted considerable attention due to the growing demand for environmental protection and sustainable economic development. − For practical applications, oxygen atoms in lignin-derived oxygenates (e.g., anisole, phenol, cresol, guaiacol, and eugenol) need to be partially or completely removed by the cleavage of various C–O bonds to produce important chemical raw feeds (e.g., benzene, toluene, and xylene (BTX)) and practically available petroleum-like biofuels . Currently, the catalytic hydrodeoxygenation (HDO) of oxygenates is regarded as an available and effective way to cope with these problems. , During the HDO process, the cleavage of C–O bonds usually goes through hydrogenation, hydrogenolysis, hydrocracking, dehydration, or decarboxylation under harsh conditions. ,,, After the reaction, a series of aromatic and aliphatic derivates can be attained. Among them, BTX compounds are especially important target products because of their extensive use and low H 2 consumption …”