Journal of Hazardous Materials 192 (2011) 1667–1674 Contents lists available at ScienceDirect Journal of Hazardous Materials jou rn al h om epage: www.elsevier.com/loc ate/jhazmat In situ incorporation of nickel nanoparticles into the mesopores of MCM-41 by manipulation of solvent–solute interaction and its activity toward adsorptive desulfurization of gas oil Abdolraouf Samadi-Maybodi a,∗ , Mohammad Teymouri b , Amir Vahid a , Aliakbar Miranbeigi c a Analytical Division, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran b Research Institute of Petroleum Industry, Tehran, Iran c Petroleum Refining Division, Research Institute of Petroleum Industry, Tehran, Iran a r t i c l e i n f o Article history: Received 20 March 2011 Received in revised form 29 June 2011 Accepted 30 June 2011 Available online 6 July 2011 Keywords: Mesoporous silica Nickel nanoparticles Adsorptive desulfurization In situ incorporation a b s t r a c t In this contribution, different amounts of nickel were incorporated into the mesopores of MCM-41 via an in situ approach. A hydrophobic nickel precursor was incorporated into the nanochannels of mesoporous silica by manipulation of solvent–solute interaction. The synthesized material was characterized using X- ray diffraction, nitrogen physisorption, temperature programmed reduction, and transmission electron microscopy. The results implicate the formation of MCM-41 with well-ordered hexagonal structure and establish also the presence of nickel nanoparticles inside the nanochannels of mesoporous silica. Adsorp- tive desulfurization of gas oil was conducted using the nickel-incorporated MCM-41 samples. The effects of nickel concentration, temperature of process and feed flow rate on the desulfurization process were examined. The MCM-41 containing 6 wt.% of nickel had both the highest breakthrough sulfur adsorption capacity and total sulfur adsorption capacity, which were 0.69 and 1.67 mg sulfur/g adsorbent, respec- tively. The breakthrough sulfur adsorption capacity was almost regained after reductive regeneration of spent adsorbent. The obtained results suggest that the method applied for the synthesis of Niy/MCM resulted in formation of well-dispersed, accessible and small nickel nanoparticles incorporated into the pores of MCM-41 which might be an advantage for adsorption of refractory sulfur compounds from low sulfur gas oil. © 2011 Elsevier B.V. All rights reserved. 1. Introduction MCM-41 is a mesoporous molecular sieve which formed from the closely packed silica-coated micelles of a surfactant template [1,2]. Because of its unique structural and physical properties; notably large surface area, tunable and large pore size, narrow pore size distribution and high thermal stability [3–5], MCM-41 has attracted great attention in many fields such as catalysis [6], separation [7], optics [8], medicine [9], and desulfurization [10,11]. But one of the main drawbacks of this material is its low activ- ity in many reactions such as acid catalyst [4,6]. This low activity can be overcome by functionalization of MCM-41 by organic and inorganic species such as metal nanoparticles, organometalic com- plexes and enzymes [6]. There are many synthetic strategies for the in situ or post-synthesis functionalization of mesoporous materi- als by metallic nanoparticles. In the former case, the most usual method is doping of reaction mélange with metal salts [12–15]. In ∗ Corresponding author. Tel.: +98 1125342350; fax: +98 1125342350. E-mail address: samadi@umz.ac.ir (A. Samadi-Maybodi). post-synthetic approach, the most common synthesis routes are I: incipient wetness impregnation [16], II: ion exchange [17], III: equi- librium adsorption [18], IV: metal complex immobilization [19], V: vapor phase deposition [20] and VI: sonication [21–24]. One of the main applications of metal-containing mesoporous silica is the desulfurization of transport fuels [25–27]. As a result of increasingly stringent environmental regulations concerning the sulfur content in transportation fuels and the heightened interest for cleaner air, refiners are facing the inevitable reality that they will soon need to produce clean automotive fuels with ultralow sul- fur levels. The current hydrotreating technology has it difficult to reduce the sulfur content in diesel to less than 10 ppmw, because the remaining refractory sulfur compounds such as dibenzothio- phene are not easy to remove [28,29]. Alternative methods such as adsorptive desulfurization, oxidative and extractive desulfuriza- tion, biodesulfurization, etc. are being developed in recent years to produce ultra low sulfur fuels. Adsorptive desulfurization of gas oil is a promising alternative to the conventional hydrodesulfurization process used on a large scale in petroleum refining industry but in most cases it cannot attain the ultra low sulfur content of below 10 ppmw [30]. Some efforts have been conducted for adsorptive 0304-3894/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2011.06.089