Orbital interactions and chemical reactivity of metal particles and metal surfaces

A review is presented with 101 refs. on chem. bonding to metal surfaces and small metal particles demonstrating the power of symmetry concepts to predict changes in chem. bonding. Ab-initio calcns. of chemisorption to small particles, as well as semiempirical extended Hueckel calcns. applied to the study of the reactivity of metal slabs are reviewed. On small metal particles, classical notions of electron promotion and hybridization are found to apply. The surroundings of a metal atom (ligands in complexes, other metal atoms at surfaces), affect bonding and reactivity through the prehybridization they induce. A factor specific for large particles and surfaces is the required localization of electrons on the atoms involved in the metal surface bond. At the surface, the bond energy is found to relate to the grou8p orbital local d. of states at the Fermi level. The use of this concept is extensively discussed and illustrated for chemisorption of CO and dissocn. of NO on metal surfaces. A discussion is given of the current decompn. schemes of bond energies and related concepts (exchange (Pauli)-repulsion, polarization, charge transfer). The role of non-orthogonality of fragment orbitals and of kinetic and potential energy for Pauli repulsion and (orbital) polarization is analyzed. Numerous examples are discussed to demonstrate the impact of those concepts on chem. bonding theor

Biosorption of Metals and Metalloids

Industrial activities such as mining operations, refining of ores and combustion of fuel oils play a relevant role in environmental pollution since their wastes contain high concentrations of toxic metals that can add significant contamination to natural water and other water sources if no decontamination is previously applied. As toxic metals and metalloids, including arsenic, cadmium, lead, mercury, thallium, vanadium, among others, are not biodegradable and tend to accumulate in living organisms, it is necessary to treat the contaminated industrial wastewaters prior to their discharge into the water bodies. There are different remediation techniques that have been developed to solve elemental pollution, but biosorption has arisen as a promising clean-up and low-cost biotechnology. Biosorption is one of the pillars of bioremediation and is governed by a variety of mechanisms, including chemical binding, ion exchange,physisorption, precipitation, and oxide-reduction. This involves operations(e.g. biosorbent reuse, immobilization, direct analysis of sample without destruction) that can be designed to minimize or avoid the use or generation of hazardous substances that have a negative impact on the environment and biota, thus following the concepts of "green chemistry" and promoting the environmental care. Furthermore, it has to be specially considered that the design of a biosorption process and the quality of a biosorbent are normally evaluated from the equilibrium, thermodynamic, and kinetic viewpoints.Therefore, a successful biosorption process can be only developed based on multidisciplinary knowledge that includes physical chemistry, biochemistryand technology, among other fields.In this chapter, we explain in detail all the aforementioned aspects. State of the art applications of biosorbents for metals and metalloids removal are carefully revised based on a complete analysis of the literature. Thus, it is evidenced in this chapter that the main points to consider regarding biosorption are the type of biomaterial (e.g. bacteria, fungi, algae, plant?derivatives and agricultural wastes, chitin/chitosan based materials) and the presence of a broad set of functional groups on their surface that are effective for the removal of different toxic metals and metalloids. In fact, removal percentages as high as 70-100% can be found in most works reported in the literature, which is demonstrating the excellent performance obtained with biosorbents. Also, biosorbents have evolved with the help of nanotechnology to modern bio-nano-hybrids materials having superlative sorption properties due to their high surface area coming from the nano-materials structures and multifunctional capacity incorporated from the several types of chemical groups of biomaterials. These, as well as other important aspects linked to biosorption are fully covered in the present chapter.Fil: Escudero, Leticia Belén. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Quintas, Pamela Yanina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Wuilloud, Rodolfo German. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Dotto, Guilherme L.. Universidade Federal de Santa Maria; Brasi