Colloids and Surfaces A: Physicochem. Eng.

Aspects 296 (2007) 222–229

A modified sol–gel process-derived highly nanocrystalline mesoporous NiO with narrow pore size distribution
Thammanoon Sreethawong a,∗ , Sumaeth Chavadej a , Supachai Ngamsinlapasathian b , Susumu Yoshikawa b

The Petroleum and Petrochemical College, Chulalongkorn University, Soi Chula 12, Phyathai Road, Pathumwan, Bangkok 10330, Thailand b Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan Received 9 May 2006; received in revised form 3 September 2006; accepted 29 September 2006 Available online 5 October 2006

Abstract Highly nanocrystalline mesoporous NiO with narrow monomodal pore size distribution was synthesized for the first time under mild conditions through a facile route of modified sol–gel process with surfactant-assisted templating technique. By controlling the hydrolysis and condensation steps of nickel methoxypropylate modified with acetylacetone in the presence of laurylamine hydrochloride surfactant aqueous solution, the nanocrystalline NiO with monomodal mesoporous characteristic could be finally attained. The synthesized material was methodically characterized by thermogravimetry and differential thermal analysis (TG–DTA), X-ray diffraction (XRD), N2 adsorption–desorption, Brunauer–Emmett–Teller (BET) surface area analysis, Barrett–Joyner–Halenda (BJH) pore size distribution analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected-area electron diffraction (SAED). The particle size of the synthesized NiO in nanosized range obtained from the SEM and TEM micrographs agreed well with the crystallite size estimated from the XRD pattern. N2 adsorption–desorption isotherm and SEM observation verified that the synthesized NiO possessed mesoporous structure. The exhibiting hysteresis pattern of the isotherm with single loop further indicated the existence of monomodal mesopore. The extremely narrow pore size distribution with mean pore diameter in the mesopore region of the synthesized NiO nanocrystal was also confirmed by the BJH analysis. © 2006 Elsevier B.V. All rights reserved.
Keywords: Nickel oxide; Nanocrystal; Mesoporous material; Surfactant template; Sol–gel process; Pore size distribution

1. Introduction Nanostructured materials that are defined as having at least one dimension between 1 and 100 nm have received steadily growing interests as a result of their peculiar and fascinating properties, and applications superior to their bulk counterparts [1]. A wealth of interesting and new phenomena associated with nanostructures have been found, with the best established examples including size-dependent excitation and emission [2–5], quantized (or ballistic) conductance [6,7], Coulomb blockade (or single-electron tunneling) [8,9], and metal-insulator transition [10]. It is commonly accepted that quantum confinement of electrons by the potential wells of nanometer-sized structures may provide one of the most powerful means to control the electrical, optical, magnetic, and thermoelectric properties

Corresponding author. Tel.: +66 2 218 4132; fax: +66 2 215 4459. E-mail address: (T. Sreethawong).

of a solid-state functional materials. Thus, the ability to generate such minuscule structures is essential too much of modern science and technology. The fabrication of nanostructured materials emphasizes not only the extremely small size, geometry, and chemical homogeneity but also the simplicity and practicability of synthesis technique. It is always recognized that the formation of a perfect crystal requires a reversible pathway between the building blocks on the solid surface and those in a fluid phase (i.e. vapor, solution, or melt). These conditions allow the building blocks to easily adopt correct positions in developing crystalline lattice. In addition, the building blocks also need to be supplied at a well-controlled rate in order to obtain crystals having homogeneous composition and uniform morphology. When developing a synthesis method for generating nanostructures, the most important issue that one needs to consider is the simultaneous control over composition and morphology [11]. Recently, nanosized materials have attracted much attention because of their unusual properties based on size-quantization effect and large surface area [12–16]. Nanosized nickel oxide

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However. Materials Nickel methoxypropylate in methoxypropanol (NMP. In addition. All chemicals were analytical grade and used without further purification.44]. Ltd. Ta2 O5 . respectively. based on our previous works. 3. For example. The sample was degassed at 200 ◦ C for 2 h to remove physisorbed gases prior to the measurement. the gel was dried overnight at 80 ◦ C to eliminate the solvents. namely TG-DTA. The mixed solution was continuously stirred at room temperature for an hour and further aged at 40 ◦ C for a day to attain sol-containing solution as a result of complete hydrolysis of the NMP precursor. Synthesis procedure Nanocrystalline mesoporous NiO was synthesized via the combined sol–gel and surfactant-assisted templating process under mild conditions. A Rigaku RINT-2100 rotating anode XRD system generating monochromated Cu K radiation with continuous scanning mode at a rate of 2◦ min−1 and operating conditions of 40 kV and 40 mA was used to obtain XRD pattern.37].T. in which a molar ratio of NMP to LAHC was adjusted to 4:1. Subsequently. the utilization of surfactant template combined with sol–gel process for the synthesis of nanosized NiO has not yet been reported. the surfactant-assisted templating sol–gel process was effectively employed to achieve nanocrystalline mesoporous TiO2 . Herein.3. as one of the relatively few metal oxides that tend to be p-type. Afterwards. Sreethawong et al. and surfactantmediated method [38]. JEOL JSM-6500FE) and a transmission electron microscope (TEM. Tokyo Chemical Industry Co. XRD. To our knowledge. the condensation reaction-induced gelation was allowed to proceed by placing the sol-containing solution into an oven at 80 ◦ C for a week to ensure complete gelation. Dy2 O3 . The mixed solution was then gently shaken until homogeneous mixing.. there are only few reports on the preparation of nanosized NiO fulfilling the requests mentioned above [39–42].05 to 0. 2. sol–gel technique [36. The obtained nanocrystalline mesoporous NiO possessed distinguished property of monomodal pore size distribution. JEOL JEM-200CX) with selectedarea electron diffraction (SAED) mode and operated at 15 and 200 kV. Hokko Chemical Industry Co. The Barrett–Joyner–Halenda (BJH) approach was used to calculate pore size distribution of the sample using the desorption data. and magnetic [23–26] properties. such as thermal decomposition [30. the nanocrystalline mesoporous NiO was synthesized via the surfactant-assisted templating sol–gel process . and In2 O3 [45–48]. a post-treatment for complete oxidation of metal particles is generally required.). Nacalai Tesque. Results and discussion In this study. A nitrogen adsorption system (BEL Japan BELSORP-18 Plus) was employed to measure adsorption–desorption isotherm at liquid nitrogen temperature of −196 ◦ C. Inc. even if this technique can be successfully used to control the porosity of synthesized materials..34]. The sample morphology was examined by a scanning electron microscope (SEM. Moreover. it is interesting to apply this combined technique to prepare nanosized NiO with specific pore size characteristic. microemulsion [32]. 0. and sensors [29]. LAHC was used as a surfactant template behaving as a mesopore-directing agent.1 M LAHC aqueous solution of pH 4. First. / Colloids and Surfaces A: Physicochem. NiO. Hence. electrochromic windows [28]. a facile preparation process that allows convenient production of these particles is necessary for practical applications. Experimental 2. the precise control of the size and distribution in nanometer regime is required. anomalous electronic [20–22]. a specified amount of analytical grade ACA was first introduced into NMP with a molar ratio of unity. The characteristic properties of nanosized NiO particles also enable one to tailor materials for a variety of applications including catalysis [17–19]. TEM. 2. probably due to the magnetic interaction [43. The characteristics of the synthesized product were systematically investigated by using several techniques. Aspects 296 (2007) 222–229 223 (NiO) is of great interest because it exhibits particular catalytic [17–19].40]. and acetylacetone (ACA.31]. Characterization techniques Simultaneous thermogravimetry and differential thermal analysis (TG-DTA. The dried sample was calcined at 500 ◦ C for 4 h to remove LAHC template and to consequently produce the desired product of mesoporous NiO nanoparticle. Shimadzu DTG-50) with a heating rate of 10 ◦ C/min in a static air atmosphere was used to study the thermal decomposition behavior of the as-prepared (dried) sample with -Al2 O3 as the reference. So far. laurylamine hydrochloride (LAHC. Because these properties can be enhanced with decreasing the particle size and are highly dependent on particle size. Eng. The Brunauer–Emmett–Teller (BET) approach using adsorption data over the relative pressure ranging from 0. thus leading to extremely packed aggregation of these nanosized particles [39. many different methods have been attempted to synthesize nanosized NiO. this work is the first attempt to synthesize NiO nanocrystal with mesoporous feature by utilizing this proposed facile technique under mild conditions. which may cause the degradation or decomposition of stabilizer used to prevent the particles from aggregation or coalescence. SEM.1. and SAED analyses. Ltd).) were used for this study. Crystalline phase present in the sample was identified by X-ray diffraction (XRD) analysis.35 was utilized to determine surface area of the sample. N2 adsorption–desorption.2 was added into the ACA-modified NMP solution. is a stable wide band gap material and can be used as a transparent p-type semiconducting layer [27]. it is difficult to synthesize well-dispersed magnetic particles in these systems because the particles have an intense tendency to strongly aggregate. Then. Recently.2. ACA serving as a modifying agent was applied to moderate the hydrolysis and condensation steps of the NMP precursor. electrochemical deposition [35]. precipitation [33. 2. in the case of wet process for preparing metal colloids successfully via liquid-phase reduction of metal salts in the presence of stabilizer.

was employed to investigate the crystallinity and purity of the prepared sample. In addition. It can be explained that when NMP is first mixed with ACA. there was no significant weight loss observed Fig. As shown in Fig. the XRD pattern of the NiO sample calcined at 500 ◦ C for 4 h reveals that the diffractogram can be determined as NiO with face-centered cubic phase. Following the mixing of ACA-modified NMP with LAHC aqueous solution. the TG–DTA results were also used to select appropriate conditions for calcining the dried sample. i.2 ◦ C plausibly due to the removal of the surfactant species bound among very tiny nickel moieties. Between this temperature range. 1 shows typical TG (a) and DTA (b) curves of the dried gel sample. Aspects 296 (2007) 222–229 in LAHC/NMP modified with ACA system. Sreethawong et al. DTA curve exhibits a dominant exothermic peak centered at 361. ACA combines with the nickel atom and one methoxypropyl group is probably abandoned. Eng. It is evident that the exothermic reaction of the surfactant molecules through oxidation is responsible for the heat release. beyond 500 ◦ C. calcination temperature and time. The sol-containing solution became rather compact gel within few hours. calcination temperature of 500 ◦ C was only selected for this preliminary study in order to demonstrate this facile and effective route for synthesis of mesoporous NiO nanocrystal with narrow pore size distribution for the first time. Thus. this peak can be assigned to the oxidative decomposition of the organic surfactant template. 2. The weight loss in the temperature range of 200–375 ◦ C is due to the burnout of organic LAHC surfactant species situated inside the mesopore of the sample. 1. After complete gelation for a week.4177 nm) owing . resulting in the subsequent suspension of these interacted species in the solution as infinitesimally colloidal solid particles or clusters. indicating that the gelation step is succeeded with a three dimensional solid network filled with a second phase of colloid dimensions. Interestingly. the mixed solution appeared opaque dark brown with precipitates due to the dispersion of partially hydrolyzed NMP molecules. It is experimentally perceptible that in the presence of ACA. either liquid or gas. Fig. After a week of incubation. The total weight loss estimated from the TG result was 52. The solution was continuously stirred at 40 ◦ C to dissolve the precipitates and to form brown sol. since the hydrolyzed NMP molecules interact with the hydrophilic head groups of micellar LAHC. which is the most useful technique for identification of crystalline structure.8 ◦ C is mainly resulted from not only the crystallization process [50] but also involved with the burnout of a small portion of organic residues as well as the dehydration and evaporation of chemisorbed water [51. the gel was dried at 80 ◦ C in an ambient environment to attain xerogel (dried NiO sample).6%. / Colloids and Surfaces A: Physicochem. resembling the case of tetraisopropyl orthotitanate (TIPT) modified with ACA system [49]. also known as the bunsenite structure (lattice constant a of cubic unit cell: 0. The thermal decomposition behavior of the as-synthesized (dried) sample was studied using TG–DTA analysis. the results from TG–DTA analysis suggest that the calcination temperature of 500 ◦ C is adequate for both complete surfactant template removal and crystallization process of the dried sample to obtain the desired nickel oxide with mesoporous structure. The exothermic peak centered at 392. but interactions are greatly dominated by short-range forces. The weight loss until temperature of 200 ◦ C is basically attributable to the removal of water physisorbed at the surface of the sample and residual solvents. Afterwards.e. the hydrolysis process of NMP with LAHC aqueous solution was much slower than that in the absence of ACA. The suspended phase is so minute that the gravitational force is negligible. (a) TG and (b) DTA curves of the as-synthesized (dried) sample. such as van der Waals attraction and surface charges.52]. which eventually resulted in NiO nanocrystal with small particle size as described later. the gelation occurs with the formation of solid fractal aggregates that gradually grow until they extend throughout the sol. the resultant gel was gradually developed into much denser phase and turned into brownish color. Because of the temperature change. Although heat treatment conditions. Therefore. exert a significant role on the properties of the ending product. One aspect of further study will be thus focused on the influence of heat treatment conditions on the physical and chemical properties of the nanocrystalline mesoporous NiO. XRD analysis.224 T. the sol–gel transition was proceeded at a mild temperature of 80 ◦ C through the condensation process between the modified NMP molecules attached with the LAHC head groups as substantiated by a formation of brown gel with dark brown liquid on the gel.

From Fig. The N2 adsorption–desorption measurement at a liquid N2 temperature of −196 ◦ C was used to study mesoporosity and textural properties of the synthesized NiO nanocrystal. Eng. 3.2 nm. The estimated crystallite size of the synthesized NiO from line broadening of (2 0 0) diffraction peak at 43. As shown in Fig. Fig. the isotherm shows a typical type IV sorption behavior with type H2 hysteresis loop. even though the calcination condition in this study was slightly more severe.2. No peaks of impurity were found in the XRD pattern. is approximately 21. XRD pattern of the nanocrystalline mesoporous NiO calcined at 500 ◦ C. the pore size distribution obtained from the BJH method by calculating from the desorption branch of the isotherm shows a very narrow monomodal distribution in the mesopore region (2–50 nm) Fig. Aspects 296 (2007) 222–229 225 Fig. the synthesized NiO possesses nanocrystalline mesoporous structure. and 79. 43. λ is the wavelength of the X-ray radiation (0. This is also a significant point to be underscored in this study. An abrupt increase in adsorption volume of adsorbed N2 was observed and located in the P/P0 value greater than 0. which is the most preferentially oriented crystal plane. / Colloids and Surfaces A: Physicochem. 75.15418 nm for Cu K ). From the N2 adsorption–desorption and XRD analyses. This sharp increase is generally associated with the capillary condensation.12 cm3 g−1 . The crystallite size of the NiO sample can be calculated using Sherrer formula [54]: L= kλ .3 m2 g−1 with BJH mean pore diameter and total pore volume of 12. and (2 2 2) crystal planes. The apparent step in the adsorption branch combined with the sharp decline in the desorption branch is an obvious indication of mesoporosity. k is the Sherrer constant usually taken as 0. respectively (JCPDS Card No. representing the mesoporous structure characteristic according to the classification of IUPAC [55]. The steepness of desorption branch verifies the uniformity of the pore diameter with very narrow distribution. clarifying the exquisite quality of the NiO nanocrystal prepared by this specific synthesis system. (a) N2 adsorption–desorption isotherm and (b) pore size distribution of the nanocrystalline mesoporous NiO calcined at 500 ◦ C.3◦ . . The result also suggests that a uniform pore structure was obtained. 3a. (2 2 0). β cos θ where L is the crystallite size. indicating that the nanocrystalline NiO obtained via this synthesis method consists of ultrapure phase.8. indicating the good homogeneity of the sample and fairly small pore size since the P/P0 position of the inflection point is related to the pore size. due to the single hysteresis loop. 2. which can be perfectly filed to (1 1 1). (2 0 0).T. and β is the full width half maximum (FWHM) of diffraction peak measured at 2θ. 3 depicts the N2 adsorption–desorption isotherm and pore size distribution of the sample. 4-0835) [53]. It is also constructive to compare the surface area of the synthesized nanocrystalline mesoporous NiO in this study with those of NiO synthesized by other techniques at similar calcination conditions. The comparison of the surface area tabulated in Table 1 reveals that the synthesized NiO possesses higher surface area than ones reported in literature.89. The textural properties of the nanocrystalline mesoporous NiO are given as follows: BET surface area of 38.6. to diffraction peaks at 37. 3b. respectively. 62. (3 1 1).4◦ .3. Sreethawong et al.2.2 nm (within mesopore region) and 0.

respectively. 500 ◦ C for 2 h. 500 ◦ C for 3 h. while irrelevant for adsorption. is very critical in the desorption processes. all of electron diffraction rings can be indexed to the cubic phase NiO. which also agree very well with XRD analysis. Calcination condition. which is well consistent with the result of XRD analysis. In a number of applications including catalysis. In consequence of N2 adsorption–desorption. The type H2 hysteresis loop is usually attributed to a difference in mechanism between condensation and evaporation processes occurring in pores with narrow necks and wide bodies. Figs. This representation can be considered as an over-simplified situation. Calcination condition. as well Fig. . According to the modern point of view [57]. often referred to as ink-bottle pores. where a vapor phase may be present at pressures above the condensation. which is equivalently in the same track as the mesoporous TiO2 nanocrystals formerly reported in several literatures [58–62]. the mesoporous structure of the synthesized NiO nanocrystal can be plausibly ascribed to the pores formed between nanocrystalline NiO particles due to their aggregation. The particle size of the sample is quite uniform in the range of approximately 15–25 nm. which obviously indicated that highly crystalline NiO crystal was formed due to the presence of apparent lattice fringes. and a liquid phase below the condensation pressure. 500 ◦ C for 4 h. / Colloids and Surfaces A: Physicochem. and it is recommended to take into account the role of network effects [56].3a 32b 31. Sreethawong et al. signifying that each grain can be considered as a single crystal. In order to obtain the insight information about the surface morphology and particle size of the sample. both SEM and TEM analyses were performed. 4.226 T. and TEM results. it is definitely worth being deduced that NiO nanoparticles with highly mesoporous texture and single crystalline structure can be attained by this synthesis technique. From the selected-area electron diffraction (SAED) pattern presented in Fig. The structure of the pore network (its connectivity and accessibility). Additionally. pore block effects. The second mechanism is related to the topology of the pore network. SEM image of the nanocrystalline mesoporous NiO calcined at 500 ◦ C. i.7c Reference This study [36] [38] Calcination condition. SEM. reactant molecules must be operated across the porous system. 5b represents high resolution TEM (HRTEM) image of the sample. Fig. 5c. Eng. Aspects 296 (2007) 222–229 Table 1 Comparison of surface area of the synthesized nanocrystalline mesoporous NiO with those of NiO synthesized by other techniques reported in literature Synthetic method Surfactant-assisted templating sol–gel method Sol Surfactant a b c Surface area (m2 /g) 38.e. 4 and 5 show the SEM and TEM images of the synthesized NiO. The relative contributions of the single-pore and pore network effects on the hysteresis loop are difficult to ascertain and indeed vary from one solid to another [56]. the observed hysteresis of the synthesized materials may be the result of two mechanisms: one is an intrinsic property of the phase transition. This is called the single-pore mechanism. The formation of NiO aggregates comprising very tiny three-dimensional disordered primary nanoparticles was visibly observed.

Sreethawong et al. this microporous structure may become easily plugged during the step of catalyst preparation. magnetic materials. the nanocrystalline monomodal mesoporous NiO prepared by the proposed surfactant-assisted templating sol–gel process can also be considered as a potential candidate for a multitude of applications. Thailand and the . Aspects 296 (2007) 222–229 227 Fig. In addition to catalysis application. such as battery cathodes. Inorganic materials with mesopores of between 2 and 50 nm play a great role in liquid separations. etc. (a) TEM image. catalytic materials. The SEM and TEM images show that the NiO nanoparticles were formed with aggregations. The N2 adsorption–desorption isotherm and BJH pore size distribution of the synthesized NiO elucidate the existence of mesoporous characteristic with very narrow monomodal pore in the mesopore region. active optical fibers. and solid oxide fuel cell (SOFC) electrodes. 4. electrochromic films. The rate of mass transfer process inside the pore depends on pore size and uniformity of pore structure. Eng.T. which is very promising for being utilized in various applications. as the reaction products have to leave the porous materials. and (c) selected-area electron diffraction (SAED) pattern of the nanocrystalline mesoporous NiO calcined at 500 ◦ C. especially if a high catalyst loading is required. p-type transparent conducting films. Acknowledgments The supports from the Petroleum and Petrochemical Consortium under the Ministry of Education. Conclusions The monomodal mesoporous NiO nanocrystal was prepared via a facile surfactant-assisted templating sol–gel route of laurylamine hydrochloride/nickel methoxypropylate modified with acetylacetone system. a high surface area feature basically relates to fine pores in structure of microporous materials (pore diameter <2 nm). gas sensors. carriers. However. 5. This is the first report on the synthesis of nanocrystalline mesoporous NiO. (b) HRTEM (high resolution TEM) image. / Colloids and Surfaces A: Physicochem. The XRD and SAED results validate that the synthesized NiO possesses crystallinity of cubic phase. For catalysis purpose. The application of the successfully synthesized nanocrystalline mesoporous NiO is also regarded as one of main targets of our future research work.

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