Elena L贸pez Maya
@ugr.es
Department of Inorganic Chemistry
IcMol, University 爋f Valencia
Scopus Publications
Scopus Publications
Mar铆a Puerto-Jim茅nez, Daniel Goma, Almudena Aguinaco, Elena L贸pez-Maya, Mayra G. 脕lvarez, Jos茅 Mar铆a Pintado, Ginesa Blanco, and Adri谩n Bogeat-Barroso
Elsevier BV
Nuria Mart铆n, Francisco G. Cirujano, Eduardo Garc铆a鈥怴erdugo, Jordi Llorca, Enrique del R铆o, Ignacio Jim茅nez鈥怣orales, Adri谩n Bogeat鈥怋arroso, Elena L贸pez鈥怣aya, and Mayra G. 脕lvarez
Wiley
AbstractThe introduction of iron ionic sites by metal exchange of defective homometallic nickel pyrazolate frameworks generates non鈥恜recious, Earth鈥恆bundant, first鈥恟ow heterometallic Fe/Ni鈥恜yrazolate frameworks. The Fe incorporation at the Ni nodes of the framework allows to control the hydrogen peroxide activation, minimizing its decomposition and O2 liberation, occurring at the homometallic Ni nodes. The generation of Fe鈭扥H reactive oxygen species at the heterometallic Fe/Ni nodes is demonstrated by the higher activity in the proof鈥恛f鈥恈oncept oxidation of 1鈥恜henylethanol to acetophenone in an aqueous medium.
Rodrigo Gil-San-Millan, Pedro Delgado, Elena Lopez-Maya, Javier D. Martin-Romera, Elisa Barea, and Jorge A. R. Navarro
American Chemical Society (ACS)
We report the controlled synthesis of thin films of prototypical zirconium metal鈥搊rganic frameworks [Zr6O4(OH)4(benzene-1,4-dicarboxylate-2-X)6] (X = H, UiO-66 and X = NH2, UiO-66-NH2) over the external surface of shaped carbonized substrates (spheres and textile fabrics) using a layer-by-layer method. The resulting composite materials contain metal鈥搊rganic framework (MOF) crystals homogeneously distributed over the external surface of the porous shaped bodies, which are able to capture an organophosphate nerve agent simulant (diisopropylfluorophosphate, DIFP) in competition with moisture (very fast) and hydrolyze the P鈥揊 bond (slow). This behavior confers the composite material self-cleaning properties, which are useful for blocking secondary emission problems of classical protective equipment based on activated carbon.
Elena L贸pez鈥怣aya, Natalia M. Padial, Javier Castells鈥怗il, Carolina R. Ganivet, Ana Rubio鈥怗aspar, Francisco G. Cirujano, Neyvis Almora鈥怋arrios, Sergio Tatay, Sergio Naval贸n, and Carlos Mart铆鈥怗astaldo
Wiley
We introduce the first example of isoreticular titanium-organic frameworks, MUV-10 and MUV-12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines to the last.聽 This enables the combination of Lewis acid titanium centers and available聽 -NH2 聽 sites in two sizeable pores for cooperative cycloaddition of CO2 聽to epoxides at room temperature and atmospheric pressure. The s elective grafting of molecules to heterometallic clusters聽 adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistry.
Francisco G. Cirujano, Elena L贸pez-Maya, Neyvis Almora-Barrios, Ana Rubio-Gaspar, Nuria Mart铆n, Jorge A. R. Navarro, and Carlos Mart铆-Gastaldo
American Chemical Society (ACS)
Zn-containing metal-organic frameworks have been used for the first time as heterogeneous catalysts in the amination of C-Cl bonds. The use of extended bis(pyrazolate) linkers can generate highly porous architectures, which favor the diffusion of amines to the confined spaces with respect to other imidazolate frameworks with narrower pore windows. The N4Zn nodes of the Zn-reticular framework show comparable activity to state-of-the-art homogeneous Zn amination catalysts, avoiding the use of basic conditions, precious metals, or other additives. This is combined with long-term activity and stability upon several reaction cycles, without contamination of the reaction product.
Rodrigo Gil-San-Millan, Elena L贸pez-Maya, Ana E. Platero-Prats, Virginia Torres-P茅rez, Pedro Delgado, Adam W. Augustyniak, Min Kun Kim, Hae Wan Lee, Sam Gon Ryu, and Jorge A. R. Navarro
American Chemical Society (ACS)
UiO-66, MOF-808 and NU-1000 metal-organic frameworks exhibit a differentiated reactivity to-wards [Mg(OMe)2(MeOH)2]4 related to the accessi-bility of the pore structure. Microporous UiO-66 remains unchanged while mesoporous MOF-808 and hierarchical micro/mesoporous NU-1000 mate-rials give rise to the formation of doped systems containing exposed MgZr5O2(OH)6 heterometallic clusters in the mesoporous cavities. This modifica-tion is responsible for a remarkable enhancement of the catalytic activity towards the hydrolytic degra-dation of P-F and P-S bonds of toxic nerve agents, at room temperature, in unbuffered aqueous solutions.
S. Tomane, E. L贸pez-Maya, S. Boujday, V. Humblot, J. Marrot, N. Rabasso, J. Castells-Gil, C. Sicard, A. Dolbecq, P. Mialane,et al.
Royal Society of Chemistry (RSC)
Correction for 鈥極ne-pot synthesis of a new generation of hybrid bisphosphonate polyoxometalate gold nanoparticles as antibiofilm agents鈥 by S. Tomane et al., Nanoscale Adv., 2019, 1, 3400鈥3405.
S. Tomane, E. L贸pez-Maya, S. Boujday, V. Humblot, J. Marrot, N. Rabasso, J. Castells-Gil, C. Sicard, A. Dolbecq, P. Mialane,et al.
Royal Society of Chemistry (RSC)
A reduced polyoxovanadate functionalized with alendronate molecules was used for the synthesis of gold nanoparticles; these hybrid nanomaterials exhibit high antibiofilm activity.
Francisco G. Cirujano, Elena L贸pez-Maya, J. A. R. Navarro, and Dirk E. De Vos
Springer Science and Business Media LLC
Well-dispersed [Pd(NH3)4]2+ sites have been introduced in the defective nickel pyrazolate porous framework, known as K@NiBDP. The resulting porous crystalline material shows a superior catalytic behavior for C鈥揘 bond formations than [Pd(NH3)4]2+ containing zeolite HY. The palladium exchanged catalyst, Pd@NiBDP, is able to promote both intra- and intermolecular hydroamination of terminal alkynes with excellent activity, reusability and selectivity towards the corresponding indole or imine versus the hydration of the alkyne. The same Pd species introduced in the microporous acid HY zeolite favors the hydration of the terminal alkyne towards the corresponding ketone, instead of the addition of the amine to the triple bond.Graphical Abstract
Francisco G. Cirujano, Elena L贸pez-Maya, Marleny Rodr铆guez-Albelo, Elisa Barea, Jorge A. R. Navarro, and Dirk E. De鈥匳os
Wiley
Copper鈥恑on鈥恊xchanged nickel pyrazolate frameworks behave as selective heterogeneous catalysts for the one鈥恜ot, two鈥恠tep (Henry reaction/Michael type addition) synthesis of neuroactive pharmaceutical intermediates starting from nitromethane and benzaldehyde. Tuning the basicity of multifunctional metal鈥搊rganic framework catalysts through ion exchange with copper(II) cations allows the tandem C鈭扖 bond鈥恌orming process to be selectively directed towards the desired pharmaceutical intermediate.
Rodrigo Gil-San-Millan, Elena L贸pez-Maya, Morgan Hall, Natalia M. Padial, Gregory W. Peterson, Jared B. DeCoste, L. Marleny Rodr铆guez-Albelo, J. Enrique Oltra, Elisa Barea, and Jorge A. R. Navarro
American Chemical Society (ACS)
The development of protective self-detoxifying materials is an important societal challenge to counteract risk of attacks employing highly toxic chemical warfare agents (CWAs). In this work, we have developed bifunctional zirconium metal-organic frameworks (MOFs) incorporating variable amounts of nucleophilic amino residues by means of formation of the mixed ligand [Zr6O4(OH)4(bdc)6(1-x)(bdc-NH2)6x] (UiO-66-xNH2) and [Zr6O4(OH)4(bpdc)6(1-x)(bpdc-(NH2)2)6x] (UiO-67-x(NH2)2) systems where bdc = benzene-1,4-dicarboxylate; bdc-NH2= benzene-2-amino-1,4-dicarboxylate; bpdc = 4,4'-biphenyldicarboxylate; bpdc-(NH2)2 = 2,2'-diamino-4,4'-biphenyldicarboxylate and x = 0, 0.25, 0.5, 0.75, 1. In a second step, the UiO-66-xNH2 and UiO-67-x(NH2)2 systems have been postsynthetically modified by introduction of highly basic lithium tert-butoxide (LiOtBu) on the oxohydroxometallic clusters of the mixed ligand MOFs to yield UiO-66-xNH2@LiOtBu and UiO-67-x(NH2)2@LiOtBu materials. The results show that the combination of pre and postsynthetic modifications on these MOF series gives rise to fine-tuning of the catalytic activity toward the hydrolytic degradation of both simulants and real CWAs in unbuffered aqueous solutions. Indeed, UiO-66-0.25NH2@LiOtBu is able to hydrolyze both CWAs simulants (diisopropylfluorophosphate (DIFP), 2-chloroethylethylsulfide (CEES), and real CWAs (soman (GD), sulfur mustard (HD)) quickly in aqueous solution. These results are related to a suitable combination of robustness, nucleophilicity, basicity, and accessibility to the porous framework.
L. Marleny Rodr铆guez-Albelo, Elena L贸pez-Maya, Said Hamad, A. Rabdel Ruiz-Salvador, Sofia Calero, and Jorge A.R. Navarro
Springer Science and Business Media LLC
The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.
Elena L贸pez-Maya, Carmen Montoro, L. Marleny Rodr铆guez-Albelo, Salvador D. Aznar鈥匔ervantes, A. Abel Lozano-P茅rez, Jos茅 Luis Cen铆s, Elisa Barea, and Jorge A. R. Navarro
Wiley
The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material.
Elena L贸pez-Maya, Carmen Montoro, Valentina Colombo, Elisa Barea, and Jorge A. R. Navarro
Wiley
The adsorptive properties of the isoreticular series [Ni 8 (OH) 4 (H 2 O) 2 (BDP_X) 6 ] (H 2 BDP_X = 1,4-bis(pyrazol-4-yl)benzene-4-X with X = H (1), OH (2), NH 2 (3)) can be enhanced by postsynthetic treatment with an excess of KOH in ethanol. In the case of X = H, NH 2 , this treatment leads to partial removal of the organic linkers, deprotonation of coordinated water molecules and introduction of extraframework cations, giving rise to materials of K[Ni 8 (OH) 5 (EtO)(H 2 O) 2 (BDP_X) 5.5 ] (1@KOH, 3@KOH) formulation, in which the original framework topology is maintained. By contrast, the same treatment with KOH in the [Ni 8 (OH) 4 (H 2 O) 2 (BDP_OH) 6 ] (2) system, enclosing the more acidic phenol residues, leads to a new material containing a larger fraction of missing linker defects and extra-framework cations as well as phenolate residues, giving rise to the material K 3 [Ni 8 (OH) 3 (EtO)(H 2 O) 6 (BDP_O) 5 ] (2@KOH), which also conserves the original face cubic centered (fcu) topology. It is noteworthy that the introduction of missing linker defects leads to a higher accessible pore volume with a concomitant increased adsorption capacity. Moreover, the creation of coordinatively unsaturated metal centers, charge gradients, and phenolate nucleophilic sites in 2@KOH gives rise to a boosting of CO 2 capture features with increased adsorption heat and adsorption capacity, as proven by the measurement of pulse gas chromatography and breakthrough curve measurements of simulated fl ue gas.
Natalia M. Padial, Elsa Quartapelle鈥匬rocopio, Carmen Montoro, Elena L贸pez, J. Enrique Oltra, Valentina Colombo, Angelo Maspero, Norberto Masciocchi, Simona Galli, Irena Senkovska,et al.
Wiley
The release of toxic pollutants into the environment, which includes oil spills, leaks of harmful industrial products, and the deliberate emission of chemical warfare agents is a risk of growing concern. Worthy of note, oil spill cleanups amount to over 10 billion dollars annually. Remediation of these environmental problems involves the use of large amounts of adsorbents such as sand, activated carbons, or zeolites. However, the effectiveness of such adsorbents is often limited by their affinity to moisture. Consequently, the search for highly hydrophobic porous materials to be used as suitable stopgap of harmful organics spills has become of paramount importance. In the past years, porous metal鈥搊rganic frameworks (MOFs) have been extensively studied to explore their possible applications in near future technologies for the safe storage of energetically and environmentally relevant gases. The tunable nature of their pores might be beneficial also in cushioning environmental problems caused by the release of harmful volatile organic compounds (VOCs). A remarkable example of the design amenability of MOFs is the well-known isoreticular [Zn4OL3] series (L= arene-dicarboxylate), wherein the size and the functionality of the pores can be modulated in a highly rational and systematic way. Nevertheless, the advantageous structural features of this family of MOFs are readily hampered by its high sensitivity to moisture, which limits its practical applications. A similar size-scaling approach has been applied by Lillerud and coworkers on the isoreticular [Zr6O4(OH)4L6] series, [9] evidencing that a significant improvement in the stability of the material can be achieved with an appropriate combination of dicarboxylate linkers and oxophylic metal fragments. Alternately, it is possible to take advantage of the enhanced stability imparted by polyazolate-containing ligands in combination with borderline metal ions. Accordingly, we designed and isolated an isoreticular series of porous MOFs, the pore size and polarity of which was modulated by coupling stiff bi-pyrazolate or mixed pyrazolate/carboxylate linkers (Scheme 1) to Ni hydroxo clusters acting as 12-connected
Publications
1) R. Gil-San-Millan, E. L贸pez-Maya, Sam GonRiu, M. Kun Wee, L. Hae Wan, and J. A. R. Navarro 鈥淢agnesium Exchanged Zirconium Metal鈥揙rganic Frameworks with Improved Detoxification Properties of Nerve Agents鈥 J. Am. Chem. Soc., 141, 11801鈭11805 (2019)
2) S. Tomane,鈥 E. L贸pez-Maya,鈥 S. Boujday, b V. Humblot, b J. Marrot,a N. Rabasso,c J. Castells-Gil,d C. Sicard,a A. Dolbecq,a P. Mialane,a and A. Vall茅e 鈥淥ne-pot synthesis of a new generation of hybrid bisphosphonate polyoxometalate gold nanoparticles as antibiofilm agents鈥 Nanoscale Advances (2019) DOI: 10.1039/C9NA00401G
3) F.G. Cirujano, E. L贸pez-Maya; J. A. R. Navarro and Dirk de Vos. Pd-Nipyrazolateframework as active and recyclable catalyst for the hydroaminationofterminal alkynes. Topics in Catalysis (2018). 6 citations
4) R. Gil-San-Millan, E. L贸pez-Maya, G. W. Peterson, J. B. DeCoste, L. M. Rodr铆guez-Albelo, E. Barea, and J. A. R. Navarro 鈥淐hemical Warfare Agents Detoxification Properties of Zirconium Metal鈥揙rganic Frameworks by Synergistic Incorporation of Nucleophilic and Basic Sites鈥 ACS Appl. Mater. Interfaces 9, 23967鈭23973 (2017). 25 citations
5) F.G. Cirujano鈥, E. L贸pez-Maya鈥, L. M. Rodr铆guez-Albelo, E. Barea , J. A. R. Navarro and Dirk de one-pot two-step C-C bond formation using MOFs with mild basicity as heterogeneous catalysts鈥. ChemCatChem, 9, 4019 鈥4023 (2017). 12 citations
6) L. M. Rodr铆guez-Albelo, E. L贸pez-Maya, S. Hamad, R. Ruiz-Salvador, S. Calero, and J. A. R. Navarro 鈥淪elective sulfur dioxide adsorption on crystal defect sites on an isoreticular Metal Organic Framework series鈥. Nat. Commun, 8, 14457 (2017). 31 citations
7) E. L贸pez-Maya, C. Montoro, L. Marleny Rodr铆guez-Albelo, Dr. Salvador D. Aznar Cervantes, Dr. A. Abel Lozano-P茅rez, Prof. Jos茅 Luis Cen铆s, E. Barea , J. A. R. Navarro. 鈥淭extile/Metal鈥揙rganic-Framework Composites as Self-Detoxifying Filters for Chemical-Warfare Agent鈥. Angew. Chem. Int. Ed. 54, 6790鈥6794, (2015). 115 citations
8) E. L贸pez-Maya, C. Montoro, V. Colombo, E. Barea, J. A. R.Navarro鈥淚mproved CO2 capture from flue gas by basic sites, charge gradients and missing linker defects on nickel fcu MOFs鈥. , 24, 6130鈥6135,(2014). 36 citations
9) N. M. Padial, E. QuartapelleProcopio, C. Montoro, E. L贸pez, J. E. Oltra, V. Colombo, A. Maspero, N. Masciocchi, S. Galli, I. Senkovska, S. Kaskel, E. Barea, J. A. R. Navarro. 鈥淗ighly HydrophobicIsoreticular Porous Metal鈥揙rganic Frameworks for the Capture of Harmful Volatile Organic Compounds鈥滱ngew. Chem. Int. Ed. 52, 8290鈥8294, (2013). 134 citations
RESEARCH OUTPUTS (PATENTS, SOFTWARE, PUBLICATIONS, PRODUCTS)
PATENTS
1) Inventors: J. A. R. Navarro, E. Barea, E. L贸pez-Maya, C. R. Maldonado, R. Gil-San Mill谩n.
Title: Adsobentesautolimpiables de compuestosorg谩nicosvol谩tilest贸xicos (Self-cleaning adsorbents of toxic volatile organic compounds).
N潞 of application: P201631713.
Date of register: 29th of December, 2016
2) Inventors: J. A. R. Navarro, E. Barea, E. L贸pez-Maya, Sam GonRiu, R. Gil-San Mill谩n.
Title: Decontaminating method of toxic chemical warfare agents by Metal-Organic Frameworks doped with magnesium hydroxide and mixtures.
N潞 of application: 10-2017-0107281
Date of register: 24th of August, 2017