Diana Y. Siberio-Pérez

Bio: Diana Y. Siberio-Pérez is an academic researcher from University of Michigan. The author has contributed to research in topics: Raman spectroscopy & Adsorption. The author has an hindex of 4, co-authored 5 publications receiving 2558 citations. Previous affiliations of Diana Y. Siberio-Pérez include University at Albany, SUNY.

A route to high surface area, porosity and inclusion of large molecules in crystals

Abstract: One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas Such materials are of critical importance to many applications involving catalysis, separation and gas storage The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m2 g(-1) (ref 2) Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m2 g(-1) (ref 3) But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m2 g(-1) (refs 4-7) Despite this, no method of determining the upper limit in surface area for a material has yet been found Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a new metal-organic framework with a surface area estimated at 4,500 m2 g(-1) This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules--attributes not previously combined in one material

Raman Spectroscopic Investigation of CH4 and N2 Adsorption in Metal−Organic Frameworks

Abstract: The adsorption behavior of CH4 and N2 (298 K, 30 bar) in a series of isoreticular metal−organic frameworks (IRMOFs) was investigated by Raman spectroscopy. For CH4, the ν1 vibrational mode shifted to lower frequency by 7.6, 8.4, 11.0, 10.3, and 10.1 cm-1 from 2917 cm-1 when adsorbed to IRMOF-1, -6, -8, -11, and -18, respectively. Along this same series, the adsorbed N2 stretch exhibited smaller shifts of 2.7, 3.1, 4.2, 4.1, and 3.7 cm-1. These shifts arise because of interactions within the framework pores, and not with the outer crystal surface. In all cases, Raman spectra at pressures up to 30 bar showed that saturation of the sorption sites does not occur. The observed shifts of the vibrational modes for each gas indicate different chemical environments within different IRMOFs, pointing to the important role the linkers play in the adsorption of gases.

Distinguishing Polymorphs of the Semiconducting Pigment Copper Phthalocyanine by Solid-state NMR and Raman Spectroscopy

Abstract: Cu(II)(phthalocyanine) (CuPc) is broadly utilized as an archetypal molecular semiconductor and is the most widely used blue printing pigment. CuPc crystallizes in six different forms; the chemical and physical properties are substantially modulated by its molecular packing among these polymorphs. Despite the growing importance of this system, spectroscopic identification of different polymorphs for CuPc has posed difficulties. This study presents the first example of spectroscopic distinction of α- and β-forms of CuPc, the most widely used polymorphs, by solid-state NMR (SSNMR) and Raman spectroscopy. 13C high-resolution SSNMR spectra of α- and β-CuPc using very-fast magic angle spinning (VFMAS) at 20 kHz show that hyperfine shifts sensitively reflect polymorphs of CuPc. The experimental results were confirmed by ab initio chemical shift calculations. 13C and 1H SSNMR relaxation times of α- and β-CuPc under VFMAS also showed marked differences, presumably because of the difference in electronic spin corre...

The Chemistry and Applications of Metal-Organic Frameworks

Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The chemistry of graphene oxide

Abstract: The chemistry of graphene oxide is discussed in this critical review Particular emphasis is directed toward the synthesis of graphene oxide, as well as its structure Graphene oxide as a substrate for a variety of chemical transformations, including its reduction to graphene-like materials, is also discussed This review will be of value to synthetic chemists interested in this emerging field of materials science, as well as those investigating applications of graphene who would find a more thorough treatment of the chemistry of graphene oxide useful in understanding the scope and limitations of current approaches which utilize this material (91 references)

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

Abstract: Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m 2 /g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.

Carbon Dioxide Capture in Metal–Organic Frameworks

Abstract: Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long