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1.
Front Chem ; 10: 865375, 2022.
Article in English | MEDLINE | ID: mdl-35372288

ABSTRACT

Experiments were carried out to research the different contents of Ga2O3 modification effects on the hydrodesulfurization (HDS) performance of 4,6-dimethyldibenzothiophene (4,6-DMDBT) catalyzed by the stepwise impregnation method. Characterization techniques such as XRD, BET, HRTEM, NH3-TPD, and Py-FTIR were performed to determine the effects of each modification of the catalyst by Ga on the properties of the prepared supports and catalysts. The catalytic effect of gallium is reflected in the fact that the empty d-orbitals of Ga elements participate in the formation of molecular orbitals in the active center and change their orbital properties, thus generating a direct desulfurization active phase suitable for complex sulfides for endpoint adsorption. The characterization results indicated that the introduction of Ga2O3 with appropriate content (2 wt.%) promoted Ni and Mo species to disperse uniformly and doping of more Ni atoms into the MoS2 crystals, which also increased the average stacking number and the length of MoS2. As a result, more NiMoS active phases were favored to form in the system. The specific surface area and the amounts of acid sites were increased, facilitating the adsorption of reactant molecules and the HDS reactions. The HDS results also suggested the effects of Ga modification play a very important role in the catalytic performance of the corresponding catalysts. The catalyst Ga-Ni-Mo/Al2O3 exhibited the highest conversion rate towards 4,6-DMDBT HDS when the amount of Ga2O3 loading was 2 wt.% with an LHSV of 2.5 h-1 at 290°C and Ga modification also can effectively improve the direct desulfurization (DDS) route selectivity in varying degrees.

2.
ACS Appl Mater Interfaces ; 14(18): 20358-20367, 2022 May 11.
Article in English | MEDLINE | ID: mdl-34460231

ABSTRACT

A non-noble-metal hybrid catalyst (Ni2P/NPC-P), composed of N,P-doped porous carbon decorated with surface P-enriched Ni2P nanoparticles, is developed to address the urgent challenges associated with mass production of clean hydrogen fuel. The synthesis features one-pot pyrolysis of inexpensive fluid catalytic cracking slurry, graphitic carbon nitride, and inorganic salts, followed by a feasible surface phosphidation process. As a non-noble metal catalyst, Ni2P/NPC-P demonstrates excellent performance in hydrogen evolution reaction in alkaline electrolytes with a low overpotential of 73 mV at a current density of 10 mA cm-2 (η10) and a small Tafel slope of 56 mV dec-1, meanwhile exhibits durability with no significant η10 change after 2000 catalytic cycles. Theoretical calculation reveals that the negatively charged P-enriched surface accelerated the rate-determining transformation and desorption of OH*. In overall water splitting, the electrocatalyst achieves a low η10 of 1.633 V, promising its potential in the cost-effective mass production of hydrogen fuel.

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