Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “pillar”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

A quantitative study of the structure-activity relationship in hierarchical zeolites using liquid-phase reactions

Micro/meso/macroporous (hierarchical) zeolites show remarkable catalytic performance for reactions involving bulky reactants. However, quantitative assessment of the microstructural characteristics contributing to the observed performance remains elusive. Here, structure–activity relationships are established for a set of micro/mesoporous self-pillared pentasil (SPP) zeolites using two parallel liquid-phase reactions (benzyl alcohol alkylation and self-etherification) based on analysis of mass transport and reaction kinetics. A reaction–diffusion mathematical model is developed that quantitatively assigns the catalytic contributions of the external surface and micropores of SPP zeolites for these reactions. In addition, the effect of the zeolite external surface structure on the corresponding catalytic activity is quantitatively assessed by comparing SPP zeolites (with MFI structure) with MCM-22 (with MWW structure). This work demonstrates that reaction–diffusion modeling allows quantitative description of the catalytic performance of hierarchical zeolites and provides a model reaction to assess nm-sized characteristic diffusion lengths in MFI.

bio-inspired↗
DOE OSTI2013

Effect of Spin-Crossover-Induced Pore Contraction on CO 2 –Host Interactions in the Porous Coordination Polymers [Fe(pyrazine)M(CN) 4 ] (M = Ni, Pt)

Variable-temperature in situ ATR-FTIR spectra are presented for the porous spin-crossover compounds [Fe(pyrazine)Ni(CN) 4 ] and [Fe(pyrazine)Pt(CN) 4 ] under CO 2 pressures of up to 8 bar. Significant shifts in the ν 3 and ν 2 IR absorption bands of adsorbed CO 2 are observed as the host materials undergo transition between low- and high-spin states. Computational models used to determine the packing arrangement of CO 2 within the pore structures show a preferred orientation of one of the adsorbed CO 2 molecules with close O=C=O···H contacts with the pyrazine pillar ligands. The interaction is a consequence of the commensurate distance of the inter-pyrazine separations and the length of the CO 2 molecule, which allows the adsorbed CO 2 to effectively bridge the pyrazine pillars in the structure. The models were used to assign the distinct shifts in the IR absorption bands of the adsorbed CO 2 that arise from changes in the O=C=O···H contacts that strengthen and weaken in correlation with changes in the Fe–N bond lengths as the spin state of Fe changes. The results indicate that spin-crossover compounds can function as a unique type of flexible sorbent in which the pore contractions associated with spin transition can affect the strength of CO 2 –host interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Cracking of Heavy Vacuum Gas Oil on Modified HY Zeolite Catalysts

Data are given on the cracking of vacuum gas oil with HY zeolite catalysts on aluminum pillared natural calcium montmorillonite under vigorous cracking conditions in laboratory reactors of different volumes with a fixed catalyst bed at 500-600°C. Increasing the cracking temperature and contact time of the vacuum gas oil with the catalyst was shown to increase the yield of the gas phase. The greatest gas yield was 42%. In this case, the gas contained C{sub 2} - C{sub 4} alkenes, including 28% propylene. We concluded that it should be possible to use aluminum pillared calcium montmorillonite as a component of a zeolite cracking catalyst for petrochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Cantilever testing of sintered-silver interconnects

Cantilever testing is an underutilized test method from which results and interpretations promote greater understanding of the tensile and shear failure responses of interconnects, metallizations, or bonded joints. The use and analysis of this method were pursued through the mechanical testing of sintered-silver interconnects that joined Ni/Au-plated copper pillars or Ti/Ni/Ag-plated silicon pillars to Ag-plated direct bonded copper substrates. Sintered-silver was chosen as the interconnect test medium because of its high electrical and thermal conductivities and high-temperature capability—attractive characteristics for a candidate interconnect in power electronic components and other devices. Deep beam theory was used to improve upon the estimations of the tensile and shear stresses calculated from classical beam theory. The failure stresses of the sintered-silver interconnects were observed to be dependent on test-condition and test-material-system. In conclusion, the experimental simplicity of cantilever testing, and the ability to analytically calculate tensile and shear stresses at failure, result in it being an attractive mechanical test method to evaluate the failure response of interconnects.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Anisotropy, size, and aspect ratio effects on micropillar compression of Al-SiC nanolaminate composites

Metal-ceramic nanolaminate composites show promise as high strength and toughness materials. Micropillar compression was used to characterize the mechanical behavior of AlSiC multilayers in different orientations including loading at 0°, 45° and 90° with respect to the direction of the layers. The 0° orientation showed the highest strength while the 45° orientation showed the lowest strength. Each orientation showed unique deformation behavior. Effects of pillar size and aspect ratio were also studied. Higher compressive strengths were observed in smaller pillars for all orientations. This effect was shown to be due to a lower probability of flaws using Weibull statistics. Additionally, changes in the aspect ratio was shown to have no significant effect on the behavior except an increase in the strain to failure in the 0° orientation. In conclusion, finite element analysis (FEA) was used to simulate and understand the effect of these parameters on the deformation behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A phenomenological dislocation mobility law for bcc metals

Dislocation motion in body centered cubic (bcc) metals displays a number of specific features that result in a strong temperature dependence of the flow stress, and in shear deformation asymmetries relative to the loading direction as well as crystal orientation. Here we develop a generalized dislocation mobility law in bcc metals, and demonstrate its use in discrete Dislocation Dynamics (DD) simulations of plastic flow in tungsten (W) micro pillars. We present the theoretical background for dislocation mobility as a motivating basis for the developed law. Analytical theory, molecular dynamics (MD) simulations, and experimental data are used to construct a general phenomenological description. The usefulness of the mobility law is demonstrated through its application to modeling the plastic deformation of W micro pillars. The model is consistent with experimental observations of temperature and orientation dependence of the flow stress and the corresponding dislocation microstructure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Investigating the compressive strength and strain localization of nanotwinned nickel alloys

Sputter deposited nickel-molybdenum-tungsten (Ni-Mo-W) thin films possess a beneficial suite of properties that stem from the extremely fine growth twins that form during the deposition process. Previously these materi- als were only characterized in tension, however, in this study in situ micropillar compression and post-mortem microstructural analysis of nanotwinned Ni 84 Mo 11 W 5 micropillars were employed to measure the compressive response and elucidate the attendant deformation mechanisms. The pillars exhibit Hookean behavior to com- pressive strengths of 3-3.5 GPa and the onset of non-linear plastic flow was manifest by discrete strain bursts and highly localized shear bands. Plastic deformation was concentrated at the top of the pillar, while the bulk of the micropillar was nominally unaffected. Post-mortem investigations indicate that at sufficiently high stresses shear banding is triggered, resulting in intense and highly localized plastic deformation that led to the formation of twin-free nanocrystalline grains within highly deformed shear bands. By contrast, the regions adjacent to the shear bands were unaffected. The absence of detwinning and dislocation glide mechanisms was unexpected and in direct contrast to what has been observed in nanotwinned Cu-Al. Post-mortem observations of the Ni-Mo-W micropillars suggest that the ultrafine twins create a unique form of dislocation starvation and source-limited plasticity. The ultrahigh compressive strength is governed by the triggering of shear bands rather than the activa- tion of dislocation glide. Finally, the specialized nature of plasticity in nanotwinned Ni-Mo-W is clear, even though the precise trigger for shear band formation in nanotwinned Ni-Mo-W remains to be identified.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Plastic-waste hydrogenolysis over two-dimensional MXene-supported ruthenium catalysts with tunable interlayer spacing

The hydrogenolysis of plastics is limited by active-site inaccessibility and inefficient mass transport of bulky polymer chains. To overcome these challenges, this work developed two-dimensional MXene-supported Ru (Ru@MXene) catalysts. Lyophilization of a solution containing dispersed MXene sheets and Ru precursors enabled the confinement of Ru species within the MXene interlayers, which act as pillars to expand the interlayer spacing. Building on this, a silica-pillared MXene-supported Ru (Ru@P-MXene) with even larger interlayer spacing exhibited a reaction rate of 914.9 g C5–C35 g Ru –1 h –1 for the hydrogenolysis of low-density polyethylene (LDPE) into valuable liquid chemicals (e.g., C 5 –C 35 ). A comparison of product yields between Ru@P-MXene and Ru@MXene suggests that elongated Ru particles confined within the MXene support expose their side facets for the reaction. In conclusion, this work demonstrates a new application of MXene in thermochemical catalysis, offering a solution to the challenges of active-site accessibility, mass transport, and reaction confinement in chemical plastic upcycling.

2D materials↗
DOE OSTI2020

Controlled 3D nanoparticle deposition by drying of colloidal suspension in designed thin micro-porous architectures

Nanoparticle deposition by drying of colloidal suspension in thin micro-porous architectures has attracted a lot of attention in scientific research as well as industrial applications. However, the underlying mechanisms of such three-dimensional (3D) deposition are not yet fully revealed due to the complexity of the co-occurring processes of two-phase fluid flows, phase change and mass transport. Consequently, the control of 3D nanoparticle deposition remains a challenge. We use a combined experimental and numerical approach to achieve controlled 3D nanoparticle deposition by drying of colloidal suspension in two pillar-based thin micro-porous architectures. By the design of pillar layout, rectangular-spiral and circular-spiral deposition configurations are obtained globally. By varying the surface wettability, vertically symmetric and sloped nanoparticle depositions can be achieved locally. While the numerical modeling reveals the mechanisms of liquid internal flow, as well as the impact of local drying rate on nanoparticle transport, accumulation and final deposition, the experimental results of deposition configurations validate the controlling strategies. This combined experimental and numerical work provides a framework to achieve desired 3D nanoparticle deposition in thin micro-porous architectures, with a thorough understanding of the underlying mechanisms of two-phase fluid flows, phase change and mass transport.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Chemical preintercalation of magnesium ions into ⍺-MoO 3 structure for improved electrochemical stability in Li-ion cells

Chemical preintercalation of layered materials, used as electrodes in intercalation-based energy storage devices, represents a promising strategy to enhance electrochemical stability and extend cycle life. However, standardized synthesis approaches for the chemical preintercalation of diverse ions into various layered materials are lacking, necessitating the development of specific synthesis routes for each ion and layered phase combination. In this study, we present the first successful demonstration of Mg 2+ ion chemical preintercalation into the interlayer region of α-MoO 3 , revealing its stabilizing effect during cycling in non-aqueous Li-ion cells. Using ethanol during hydrothermal treatment facilitated molybdenum reduction, which was critical for Mg 2+ ion preintercalation. Interestingly, we found that Mg preintercalation was accompanied by the incorporation of water. Mg-preintercalated α-MoO 3 exhibited enhanced charge storage capacity, electrochemical stability, and power capability compared to pristine α-MoO 3 electrodes. This improved performance is attributed to the structural stabilization provided by Mg 2+ pillars, which prevent undesirable phase transformations during repeated Li intercalation/deintercalation, and increased Li + ion diffusion due to the shielding of electrostatic interactions between electrochemically cycled ions and the α-MoO 3 lattice, enabled by structural water. In conclusion, our study offers new insights into developing chemical preintercalation synthesis approaches that can be broadly applied to a wide range of pillaring ions and layered material hosts.

25 ENERGY STORAGE↗
DOE OSTI2016

A dislocation-based crystal viscoplasticity model with application to micro-engineered plasma-facing materials

We report materials developed with special surface architecture are shown here to be more resilient to the transient thermomechanical environments imposed by intermittent exposures to high heat flux thermal loading typical of long-pulse plasma transients. In an accompanying article, we present experimental results that show the relaxation of residual thermal stresses in micro-engineered W surfaces. A dislocation-based model is extended here within the framework of large deformation crystal plasticity. The model is applied to the deformation of single crystals, polycrystals, and micro-engineered surfaces composed of a uniform density of micro-pillars. The model is utilized to design tapered surface micro-pillar architecture, composed of a Re core and W coatings. Residual stresses generated by cyclic thermomechanical loading of these architectures show that the surface can be in a compressive stress state, following a short shakedown plasma exposure, thus mitigating surface fracture.

36 MATERIALS SCIENCE↗
DOE OSTI2012

A 3D complex containing novel 2D Cu{sup II}-azido layers: Structure, magnetic properties and effects of 'Non-innocent' reagent

A novel copper-azido coordination polymer, [Cu{sub 2}(N{sub 3}){sub 3}(L)]{sub n} (1, HL=pyrazine-2-carboxylic acid), has been synthesized by hydrothermal reaction with 'Non-innocent' reagent in the aqueous solution. In the reaction system, Cu{sup II} ions are avoided to reduce to Cu{sup I} ions due to the existence of Nd{sup III}. It is found that the complex is a 3D structure based on two double EO azido bridged trimmers and octahedron Cu{sup II} ions, in which the azide ligands take on EO and {mu}{sub 1,1,3} mode to form Cu{sup II}-azido 2D layers, furthermore L ligands pillar 2D layers into an infinite 3D framework with the Schlaefli symbol of {l_brace}4;6{sup 2}{r_brace}4{l_brace}4{sup 2};6{sup 12};8{sup 10};10{sup 4}{r_brace}{l_brace}4{sup 2};6{sup 4}{r_brace}. Magnetic studies revealed that the interactions between the Cu{sup II} ions in the trimmer are ferromagnetic for the Cu-N-Cu angle nearly 98 Degree-Sign , while the interactions between the trimmer and octahedron Cu{sup II} ion are antiferromgantic and result in an antiferromagnetic state. - Graphical abstract: A 3D complex containing novel 2D Cu{sup II}-azido layers, [Cu{sub 2}(N{sub 3}){sub 3}(L)]{sub n} (HL=pyrazine-2-carboxylic acid), was synthesized by hydrothermal reaction and exhibit interesting structure and magnetic properties. Highlights: Black-Right-Pointing-Pointer 'Non-innocent' reagents plays a key role in the process of formation of this complex. Black-Right-Pointing-Pointer 2D layer is formed only by Cu{sup II} ions and azido ligands. Black-Right-Pointing-Pointer Pyrazine-2-carboxylate ligands reinforce 2D layers and pillar them into an infinite 3D framework. Black-Right-Pointing-Pointer Magnetic study indicates that alternating FM-AF coupling exists in the complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

{pi}-{pi} Interactions and magnetic properties in a series of hybrid inorganic-organic crystals

The series of hybrid inorganic-organic solids T(Im){sub 2}[Ni(CN){sub 4}] with T=Fe, Co, Ni and Im=imidazole were prepared by soft chemical routes from aqueous solutions of the involved building units: imidazole, T{sup 2+} metal and the [Ni(CN){sub 4}]{sup 2-} anionic block. The obtained samples were characterized from infrared and UV-vis spectroscopies, and thermogravimetric, X-ray diffraction and magnetic measurements. Anhydrous solids which crystallize with a monoclinic unit cell, in the I2/a space group with four formula units per cell (Z=4) were obtained. Their crystal structure was solved ab initio from the recorded X-ray powder patterns and then refined by the Rietveld method. The metal T is found with octahedral coordination to four N ends of CN groups and two imidazole molecules while the inner Ni atom preserves its planar coordination. The system of layers remains stacked in an ordered 3D structure through dipole-dipole and {pi}-{pi} interactions between imidazole rings from neighboring layers. In this way, a pillared structure is achieved without requiring the coordination of both nitrogen atoms from imidazole ring. The recorded magnetic data indicate the occurrence of a predominant ferromagnetic interaction at low temperature for Co and Ni but not for Fe. Such magnetic ordering is more favorable for Ni with transition temperature of 14.67 K, which was ascribed to the relatively high polarizing power for this metal. Within the considered T metals, to nickel the highest electron-withdrawing ability corresponds and this leads to an increase for the metal-ligand electron clouds overlapping and to a stronger {pi}-{pi} attractive interaction, two factors that result into a higher magnetic ordering temperature. - Graphical Abstract: Magnetic ordering through the {pi}-{pi} interaction between the imidazole rings. Highlights: Black-Right-Pointing-Pointer Hybrid inorganic-organic solids. Black-Right-Pointing-Pointer Hybrid inorganic-organic molecular based magnets. Black-Right-Pointing-Pointer Ferromagnetic interaction through {pi}-{pi} stacking of imidazole rings. Black-Right-Pointing-Pointer Organic pillars formed through {pi}-{pi} stacking.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites with excellent decolorization performance

Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled in the presence of CTAB, and subsequently pillared with Keggin ions. The obtained CTAB-Al-MO with the basal spacing of 1.59 nm could be stable at 300 Degree-Sign C for 2 h and also possesses high total pore volumes (0.41 cm Superscript-Three g{sup -1}) and high specific BET surface area (161 m{sup 2} g{sup -1}), which is nine times larger than that of the pristine (19 m{sup 2} g{sup -1}). Possible formation process for the highly thermal stable CTAB-Al-MO is proposed here. The decolorization experiments of methyl orange showed that the obtained CTAB-Al-MO exhibit excellent performance in wastewater treatment and the decolorization rate could reach 95% within 5 min. - Graphical Abstract: Well-ordered organic-inorganic hybrid LMO nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled by CTAB, and subsequently pillared with Keggin ions. Highlights: Black-Right-Pointing-Pointer A two-step synthesis method was used to prepare the CTAB-Al-MO. Black-Right-Pointing-Pointer The CTAB-Al-MO has the large basal spacing and high specific BET surface area. Black-Right-Pointing-Pointer The thermal stability of the well-ordered CTAB-Al-MO could obviously improve. Black-Right-Pointing-Pointer The CTAB-Al-MO exhibits excellent oxidation and absorption ability to remove organic pollutants.

36 MATERIALS SCIENCE↗
DOE OSTI2013

4,4′-Bipyridine-aided synthesis and characterization of Zn(II) and Cd(II) 2-sulfoterephthalate complexes

Six d{sup 10} complexes, [Zn{sub 1.5}(stp)(bpy){sub 0.5}(H{sub 2}O){sub 2}]·0.5H{sub 2}O (1), Cd{sub 1.5}(stp)(bpy){sub 0.5}(H{sub 2}O){sub 2} (2), [Cd{sub 1.5}(stp)(bpy)(H{sub 2}O)]·H{sub 2}O (3), [Zn{sub 0.5}(bpy){sub 0.5}(H{sub 2}O){sub 2}][Zn(stp)(bpy)(H{sub 2}O)]·0.5H{sub 2}O (4), Cd{sub 3}(stp){sub 2}(bpy){sub 3}(H{sub 2}O){sub 3} (5), Hbpy·[Zn{sub 0.5}(bpy)(H{sub 2}O){sub 2}][Zn{sub 0.5}(stp)(H{sub 2}O)]·H{sub 2}O (6) based on 2-sulfoterephthalate (stp{sup 3−}) and 4,4′-bipyridine (bpy) have been synthesized under hydro/solvo-thermal conditions and structurally characterized. Complex 1 exhibits a three-fold interpenetrated 3D porous architecture. Complexes 2 and 3 possess helices with different chirality arranging alternately. 4 and 6 are addition compounds, which compose of complex cation and complex anion. Complex 5 features a 3D layer-pillar framework in which a (4, 4) grid layer is constructed by stp{sup 3−} ligands and Cd(II) ions, and the layers are further connected by bpy pillars. The solid-state luminescent properties of the coordination polymers have also been investigated. - Graphical abstract: Display Omitted - Highlights: • Complexes 1–3 possess helices with different chirality arranging alternately. • The structural diversity can be attributed to various coordination modes of ligands. • The formation of helical structure is related to the adjacent carboxyl and sulfonate groups. • Bpy exhibits three roles: bridge, hydrogen bonding acceptor, and template.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

A series of novel metal–organic coordination polymers constructed from the new 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole spacer and aromatic carboxylates: Synthesis, crystal structures, and luminescence properties

Using bifunctional organic ligand 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HL) and different aromatic carboxylates as secondary ligands, four novel metal-organic coordination polymers, [Zn(L)(1,4-bdc){sub 0.5}] (1), [Zn{sub 1.5}(L)(2,5-pydc)] (2), [Zn(HL)(1,2,4,5-btec){sub 0.5}] (3), and [Cd(HL)(1,2,4,5-btec){sub 0.5}] (4) (1,4-bdc, 1,4-benzenedicarboxylate; 2,5-pydc, 2,5-pyridinedicarboxylate; 1,2,4,5-btec, 1,2,4,5-benzenetetracarboxylate) have been successfully synthesized and analyzed. Compound 1 features the 2D [Zn(L)]{sub n} layers built by μ{sub 3}-L bridging ligands and Zn(II) ions, which are further linked by pillared 1,4-bdc{sup 2−} ligands to form a 2-fold interpenetrating dmc framework. The 3D network of compound 2 can be simplified as a rare 2-nodal (3,6)-connected rtl (rutile) topology. Compound 3 possesses a 2D layer structure which is accomplished by connecting ladder-chains to L ligands. Compound 4 exhibits 2D [Cd(1,2,4,5-btec)] layers with infinite Cd–O–Cd rods and the adjacent 2D networks are further pillared by L with terminal bidentate coordination mode to generate the final 3D structure. The solid-state luminescent studies show that compounds 1–4 display intense fluorescent emissions. - Graphical abstract: Using bifunctional organic ligand 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HL) and different aromatic carboxylates as secondary ligands, four novel metal-organic coordination polymers have been obtained. All compounds show good luminescence properties at room temperature. Display Omitted - Highlights: • Four Zn(II)/Cd(II)-MOCPs have been successfully prepared with the rigid bifunctional ligand 5-(4-imidazol -1-yl-phenyl) -2H-tetrazole and different aromatic carboxylates mixed ligands. • Compound 2 is a 2-nodal rtl (rutile) net and compound 4 is a binodal (5, 6)-connected net with yav topology. • Compounds 1-4 display intense fluorescent emissions at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Tuning the formations of metal-1,3,5-benzenetricarboxylate frameworks via the assistance of amino acids

Seven new metal-1,3,5-benzenetricarboxylate coordination polymers have been synthesized by modification of auxiliary components during the assembly reactions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by XRD and TGA. Interestingly, they show fascinating topological structures. Compounds 1 and 2 possess the undulating layer structure with 3-connected hcb network and (3,6)-connected kgd network. Compound 3 possesses three-dimensional (3D) pillared-layer structure with 3-connected 2-fold interpenetrating srs net. Compound 4 also has the 3D 2-fold interpenetrating pillared-layer structure; however, it has (3,5)-connected hms topology because the Cd(II) center is 5-connected. Compound 5 possess 3D structure through hydrogen bonding interactions between ladder-like layers. Compounds 6 and 7 have the similar 3D frameworks with 4-connected umc net and (3,7)-connected (3.4.5)(3{sup 2}.4{sup 6}.5{sup 5}.6{sup 8}) topology, respectively. The photoluminescent properties of compounds 2–7 were also investigated. - Graphical abstract: Presented here are seven new metal-1,3,5-benzenetricarboxylate coordination polymers with diverse structures from 2D layers to 3D open frameworks. The synthesis and structural diversity of these compounds are determined by the additional amino acids as unusual buffering agents. - Highlights: • Structural diversity of metal-1,3,5-benzenetricarboxylate frameworks. • Tuning structural topologies of MOFs via the assistance of amino acids. • Amino acids as unusual buffering agents for the synthesis of MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Synthetic and structural investigations of mercurous and mercuric organophosphonates and phenylarsonates

The following twelve mercurous and mercuric organophosphomates, bis/diphosphonates and phenylarsonates have been isolated and structurally characterized by single crystal X-ray diffraction, {sup 13}C-and {sup 31}P NMR, infrared and Raman spectroscopic methods: Hg{sub 2}(HO{sub 3}PC{sub 6}H{sub 5}){sub 2}(1), Hg{sub 2}(HO{sub 3}P(C{sub 6}H{sub 4})PO{sub 3}H)(2), Hg{sub 2}(HO{sub 3}P(C{sub 6}H{sub 4}){sub 2}PO{sub 3}H)(3), Hg{sub 2}(HO{sub 3}P(CH{sub 2}){sub 4}PO{sub 3}H)(4), Hg{sub 2}(O{sub 3}PC{sub 6}H{sub 5})·H{sub 2}O(5), (Hg{sub 2}){sub 2}(O{sub 3}P(CH{sub 2}){sub 2}PO{sub 3})(6), (Hg{sub 2}){sub 2}(O{sub 3}P(CH{sub 2}){sub 3}PO{sub 3})(7), Hg(O{sub 3}PC{sub 6}H{sub 5})·H{sub 2}O(8), Hg(O{sub 3}PCH{sub 2}C{sub 6}H{sub 5})·H{sub 2}O(9), Hg(O{sub 3}AsC{sub 6}H{sub 5})·H{sub 2}O(10), Hg{sub 3}(O{sub 3}AsC{sub 6}H{sub 5}){sub 2}(HO{sub 3}AsC{sub 6}H{sub 5}){sub 2}(11) and (Hg{sub 2})Hg{sub 3}(O{sub 3}P(C{sub 6}H{sub 4})PO{sub 3}){sub 2}·2H{sub 2}O(12). Compounds 1–7 are the first examples of mercurous phosphonates and di/bisphosphonates. They contain Hg{sub 2}O{sub 6} units, which consist of Hg{sub 2}{sup 2+} cations with Hg-Hg bond of ~2.5 Å length. Phenylphosphonates 1 and 5 are layered compounds, whereas bis/diphosphonates 2, 3, 4, 6 and 7 have pillared-layered and three-dimensional structures. Compounds 8–11 are layered mercuric phosphonates and phenylarsonates. Compound 12 is a three-dimensional mixed-valent mercury phenylenebisphosphonate. - Graphical abstract: The first examples of mercurous organophosphonates and organodiphosphonates have layered, pillared-layered and three-dimensional structures.

36 MATERIALS SCIENCE↗