José Jiménez-Jiménez

Surfactant‐Assisted Synthesis of a Mesoporous Form of Zirconium Phosphate with Acidic Properties

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Luminescent carbon nanoparticles: effects of chemical functionalization, and evaluation of Ag+ sensing properties

Luminescent carbon-based nanoparticles, addressed as carbon dots (CDs), were synthesized at relatively low temperature from lactose following an easy and inexpensive procedure. Modification of their surface was done by functionalization with mercaptosuccinic acid (MSA) (CDs–MSA). Transmission electron microscopy images showed regular spherical nanoparticles of 5 nm diameter. Raw and functionalized (CDs–MSA) CDs were highly fluorescent at 448 and 472 nm, with relative high quantum yield (Φ = 0.21 and 0.46 respectively). At the maximum fluorescence of CDs–MSA the intensity was quenched by addition of Ag+ ions by a static mechanism with a Stern–Volmer constant of 3.7 × 103 M−1. The analysis of the emission spectra showed that the CD–MSA complex was stable after this process. The quenching profiles showed that only 44% of the CD–MSA fluorophores are accessible to Ag+. The main figures of merit were detection and quantification limits of 385.8 nM and 1.2 μM respectively, and the precision as relative standard deviation was 1.76%. No interference was observed when other metal ions were present indicating a high selectivity for Ag+ detection. The results showed that CDs–MSA can be used for efficient quantification of Ag+ in silver nanoparticle dissolution.

Proton conductivity of mesoporous MCM type of zirconium and titanium phosphates

Abstract A family of novel mesoporous zirconium(IV) and titanium(IV) phosphate materials has been prepared by sol-gel synthesis in the presence of cetyltrimethylammonium bromide, a structure-directing cationic surfactant. The solids obtained after removal of the surfactant by acid-ethanol extraction or by calcination have high BET surface areas of 240–330 m2g−1 and a narrow pore size distribution in the mesopore range. AC conductivity measurements of these solids were carried out by impedance spectroscopy. The data indicate that two electric relaxation processes are present; one at low frequency, associated with the grain boundary and one at higher frequency related to a relaxation within the pores. Although a partial contribution of electronic conduction cannot be excluded, the major contribution comes from proton mobility along the channels.

Synthesis and characterisation of acid mesoporous phosphate heterostructure (PPH) materials

New stable acid mesoporous phosphate heterostructure materials, consisting of expanded zirconium phosphate with silica galleries, have been prepared using as precursor MCM-50 type lamellar zirconium phosphate, expanded with cetyltrimethylammonium as the surfactant, hexadecylamine as the co-surfactant, and tetraethylorthosilicate (TEOS) as the silica source. The amounts of co-surfactant and TEOS employed play a crucial role in the textural and acidic properties of the mesostructures. The obtained solids present a strong Bronsted acidity as deduced by the formation of iso-derivatives in the 1-butene isomerisation test.

Fluorescent sensor for Cr(VI) based in functionalized silicon quantum dots with dendrimers

Highly luminescent nanoparticles based in Silicon quantum dots, coated by hydroxyl PAMAM dendrimer (PAMAM-OH) of 5th generation, were obtained by one step process by hydrothermal treatment of 3-Aminopropyl)triethoxysilane (APTES) in aqueous solution. Previous to the optimization of the synthesis procedure, different dendritic molecules of 5th generation were tested to obtain the most intense fluorescence signal. The influence of different parameters such ratio APTES/PAMAM-OH, pH and ionic strength on the fluorescence intensity was studied. The fluorescence spectra showed maximum excitation and emission wavelengths at 370 and 446 nm, respectively. The obtained silicon nanoparticles (SiQDs@PAMAM-OH) were characterized by TEM, DLS and XPS, and were found to detect selectively Cr(VI) in aqueous solutions at 2.7 μM level of detection, sensitivity of 0.2 μM with a RSD of 0.16% (n=10). To study the feasibility of the proposed system for Cr(VI) detection, it was tested in real electrochemical solution bath and a tanning effluent obtained from electrochemical industry and with two certified waters, demonstrating promising outcomes as nano-sensor.

Evaluation of Cu-PPHs as active catalysts for the SCR process to control NOx emissions from heavy duty diesel vehicles

Copper based catalysts supported on mesoporous materials, which were in turn based on a surfactant expanded zirconium phosphate for the formation of silica galleries in the interlayer space, were prepared by the impregnation method. They were then characterised and tested in the selective catalytic reduction of NO with ammonia as active catalysts for the control of the NOx emissions from heavy duty vehicles. Copper catalysts displayed a high catalytic performance, even in the presence of 14% (v/v) of H2O and 100 ppm of SO2. They also displayed improved catalytic behaviour when compared to a CuZSM5 catalyst.

Microwave-assisted synthesis of carbon dots and its potential as analysis of four heterocyclic aromatic amines

Fluorescent water soluble carbon nanoparticles, in short carbon dots (CDs), was synthesized from lactose by microwave assisted hydrochloric acid method. Characterized by TEM and DLS to obtain the morphology shape (average 10nm in size), with a higher negative surface charge supported by the composition was obtained by XPS spectroscopy. The maximum of the emission was centered at 450 nm with a lifetime of 2.1 ns. Without further functionalization of the CDs a nanosensor was obtained that responded exponentially to HAAs in the 0.35-0.45 mg L(-1) concentration range by fluorescence static quenching, demonstrated by the lifetime analysis of the CDs in presence of HAAs. Some amino compounds were selected as model for interferences to evaluate the selectivity of this method, showing a notorious added value, with recoveries around 98%. The accuracy of the method was in terms of RSD about 2.5%. The results suggest their promising applications in chemical sensing.

Fluorescent chemosensor for pyridine based on N-doped carbon dots

Fluorescent carbon dots (CDs) and its nitrogen doped (N-CDs) nanoparticles have been synthesized from lactose as precursor using a bottom-up hydrothermal methodology. The synthesized nanoparticles have been characterized by elemental analysis, FTIR, Raman, TEM, DLS, XPS, and steady-state and life-time fluorescence. The synthesized carbon nanoparticles, CDs and N-CDs, have a size at about 7.7±2.4 and 50±15nm, respectively, and quantum yields of 8% (CDs) and 11% (N-CDs). These techniques demonstrated the effectiveness of the synthesis procedure and the functionalization of the CDs surface with amine and amide groups in the presence of NH3 in aqueous media. The effect of excitation wavelength and pH on the luminescent properties was studied. Under the optimal conditions, the nitrogen doped nanoparticles can be used as pyridine sensor in aqueous media because they show an enhancement of its fluorescence with a good linear relationship. The analytical method is simple, reproducible and very sensitive for pyridine determination.

Tungstotellurates of the imidazolium and 4-methylimidazolium cations

Tungstotellurates of the organic imidazolium and 4-methyl-imidazolium cations have been prepared and characterized by X-ray diffraction and i.r. spectroscopy. The [TeW6O24]6− anion is formed by close packing of oxygen atoms with Te and W atoms in distorted octahedral voids. In both compounds the organic cations are involved in hydrogen bonds, to the [TeW6O24]6− anion in [H2imz]6[TeW6O24] · 2(Himz) (1) and to Te(OH)6 units in [4-H2-methyl-imz]6[TeW6O24] · Te(OH)6 (2). Solution studies of (1) and (2) by 1H-, 183W- and 125Te-n.m.r. have been carried out. Thermogravimetric (t.g.) and calorimetric (d.s.c.) analyses were performed for both compounds.

Fingerprint detection and using intercalated CdSe nanoparticles on non-porous surfaces

A fluorescent nanocomposite based on the inclusion of CdSe quantum dots in porous phosphate heterostructures, functionalized with amino groups (PPH-NH2@CdSe), was synthesized, characterized and used for fingerprint detection. The main scopes of this work were first to develop a friendly chemical powder for detecting latent fingerprints, especially in non-porous surfaces; their further intercalation in PPH structure enables not to spread the fluorescent nanoparticles, for that reason very good fluorescent images can be obtained. The fingerprints, obtained on different non-porous surfaces such as iron tweezers, mobile telephone screen and magnetic band of a credit card, treated with this powder emit a pale orange luminescence under ultraviolet excitation. A further image processing consists of contrast enhancement that allows obtaining positive matches according to the information supplied from a police database, and showed to be more effective than that obtained with the non-processed images. Experimental results illustrate the effectiveness of proposed methods.