Nitrogen-rich carbon-supported ultrafine MoC nanoparticles for the hydrotreatment of oleic acid into diesel-like hydrocarbons

Wang, Fei; Zhang, Wenjuan; Jiang, Jianchun; Xu, Jie; Zhai, Qiaolong; Wei, Linshan; Long, Feng; Liu, Chao; Liu, Peng; Wang, Tan; He, Daheng

doi:10.1016/j.cej.2019.122464

Cited by 55 publications

(18 citation statements)

References 71 publications

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“…To simplify the calculation model, MoC (001) facet was selected for the calculations because the (001) facet of Mo-terminated MoC is often used as the representative facet of MoC to discuss calculation-related issues qualitatively. [36] The selection agrees well with the observation of the exposed (001) facet of MoC in Figure S6f in the Supporting Information. Moreover, the possibility of (N-doped) porous graphene adsorption on the surface of MoC (110) facet was also explored.…”

Section: Methodssupporting

confidence: 85%

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH₄ Production

Han

Liu

et al. 2021

Advanced Energy Materials

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for improving the properties of catalysts and controlling catalysis. However, this modulation is of atomic-level precision and thus extremely difficult.Herein, we have successfully modified the coordination environment of active sites on the surfaces of MoC nanoparticles by anchoring pyridinic N atoms of porous graphene on Mo atoms adjacent to hollow sites, passivating the hollow sites and activating top sites of Mo atoms. MoC and its related materials have been widely used to catalyze various reactions, [3][4][5][6][7][8] of which the electrocatalytic hydrogen evolution reaction (HER) and the electrocatalytic reduction of CO 2 (CO 2 ECR) are both green processes to produce fuels for energy production use. The MoC family has exhibited excellent abilities to catalyze the HER, [6][7][8] which are significant breakthroughs showing the potential of the MoC-related materials for electrocatalysts and energy researches. However, for CH 4 , one of CO 2 ECR products, which has also attracted great attention for its compatibility with existing infrastructure and potential substitution for fossil fuels, the difficult removal of adsorbed OH (denoted as *OH) from the active sites of the MoC family causes their reported Faradaic efficiency (FE) to be no larger than 0.1%. [8] That is much Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis. However, this may be a highly challenging procedure. Guided by the first-principles calculations, the modification of the coordination environment of active sites on MoC nanoparticle surfaces is experimentally accomplished by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites′ affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites, and reduces the overadsorption of OH on the Mo active sites, as predicted by calculations. The atomic-level modification is well confirmed by atomicresolution imaging, high-resolution electron tomography, synchrotron soft X-ray spectroscopy, and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO 2 reduction to CH 4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolytes. It also exhibits a negligible activity loss over 50 h.

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Section: Methodssupporting

confidence: 85%

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH₄ Production

Han

Liu

et al. 2021

Advanced Energy Materials

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“…First, most of the 3d metal-modified Mo x C catalysts were applied in electrocatalysis or thermocatalysis, while their catalytic performance in selective hydrogenation at low temperatures (<100 °C) has rarely been reported. Additionally, current Mo x C-based catalysts were synthesized mainly through a traditional temperature-programmed carburization method, which normally exhibited a low surface area and large nanoparticles. − …”

Section: Introductionmentioning

confidence: 99%

Molybdenum Carbide-Promoted Cobalt as an Efficient Catalyst for Selective Hydrogenation

Liu

Cao

Yang

et al. 2020

Ind. Eng. Chem. Res.

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Developing heterogeneous catalysts for hydrogenation under mild conditions is industrially significant, but there still remain some challenges in the preparation of inexpensive and highly active catalysts. Herein, we present Co-Mo x C catalysts prepared by a one-pot pyrolysis method for which excellent catalytic performance toward selective hydrogenation is achieved. The highest turnover frequency (TOF) of nitrobenzene hydrogenation reached up to 105.3 h −1 with a selectivity of higher than 99% at 60 °C. As evidenced by our experiment and analysis, the electronic structure of cobalt can be affected by the in situ-formed molybdenum carbide, which led to an improved dispersion via the interaction between Co and Mo x C as well as advanced catalytic performance. These results could provide some potential for the design of efficient hydrogenation catalysts for further industrial applications.

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“…When compared to other sources of biomass, such as woody biomass, oils have an advantage when considering hydrocarbon production. Previous studies have shown that fatty acids can be converted to hydrocarbons through deoxygenation reactions, [1][2][3][4][5][6][7] whereas compounds found in other types of biomass, such as phenolic compounds or sugars lead to coke formation. 8 Vegetable oils are very interesting candidates when considering the production of high-quality fuels, such as jet fuel and rocket fuels, since they show extremely low levels of undesired elements (e.g., sulfur, nitrogen, and heavy metals).…”

Section: Introductionmentioning

confidence: 99%

Effects of reaction parameters on the deoxygenation of soybean oil for the sustainable production of hydrocarbons

Pimenta

Barreto

Santos

et al. 2020

Env Prog and Sustain Energy

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Hydrotreating of vegetable oils offers a green alternative to oil‐derived fuels and raw hydrocarbon materials, usually obtained from oil. In contrast to sulfided catalysts, which contaminate the product with sulfur, carbide‐based catalysts are able to produce clean hydrocarbons. A NiMo carbide‐based catalyst, supported on nanometric γ‐alumina was prepared, characterized by X‐ray crystallography, Nitrogen physisorption, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and Raman spectroscopy. The oxidation temperatures and acidity were also determined. Tests were performed in a batch‐type reactor for the hydrotreatment of soybean oil at 360, 380, and 400°C and 4.5 MPa. Liquid samples were analyzed by gas chromatography with a mass spectra detector. The reaction rate was calculated showing that reactant concentration did not influence deoxygenation rates, nor did the catalyst revealed a significant change in the activity. The product composition was extensively characterized, proving that reaction temperature greatly influences the concentration of aromatic, unsaturated and saturated hydrocarbons, as well as chain size distributions.

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Nitrogen-rich carbon-supported ultrafine MoC nanoparticles for the hydrotreatment of oleic acid into diesel-like hydrocarbons

Cited by 55 publications

References 71 publications

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH₄ Production

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH₄ Production

Molybdenum Carbide-Promoted Cobalt as an Efficient Catalyst for Selective Hydrogenation

Effects of reaction parameters on the deoxygenation of soybean oil for the sustainable production of hydrocarbons

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Nitrogen-rich carbon-supported ultrafine MoC nanoparticles for the hydrotreatment of oleic acid into diesel-like hydrocarbons

Cited by 55 publications

References 71 publications

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH4 Production

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH4 Production

Molybdenum Carbide-Promoted Cobalt as an Efficient Catalyst for Selective Hydrogenation

Effects of reaction parameters on the deoxygenation of soybean oil for the sustainable production of hydrocarbons

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Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH₄ Production

Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH₄ Production