Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity

We report the synthesis, structural characterization, and functionality of an open-framework hybrid that combines Ca2+ ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl) isophthalic acid (PiPhtA). Ca-PiPhtA-I is obtained by slow crystallization at ambient conditions from acidic (pH≈3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data.All connectivity modes of the “parent” Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca PiPhtA-I is 5.7 ×10−4 S·cm−1. It increases to 1.3 × 10−3 S·cm−1 upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10−3 S·cm−1, measured at 98% RH and T = 24 °C. Ea for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction.Proyecto nacional MAT2010-1517

Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns

Electrochemical conversion of CO₂ holds promise for utilization of CO₂ as a carbon feedstock and for storage of intermittent renewable energy. Presently Cu is the only metallic electrocatalyst known to reduce CO₂ to appreciable amounts of hydrocarbons, but often a wide range of products such as CO, HCOO^–, and H₂ are formed as well. Better catalysts that exhibit high activity and especially high selectivity for specific products are needed. Here a range of bimetallic Cu–Pd catalysts with ordered, disordered, and phase-separated atomic arrangements (Cu_at:Pd_at = 1:1), as well as two additional disordered arrangements (Cu3Pd and CuPd3 with Cu_at:Pd_at = 3:1 and 1:3), are studied to determine key factors needed to achieve high selectivity for C1 or C2 chemicals in CO₂ reduction. When compared with the disordered and phase-separated CuPd catalysts, the ordered CuPd catalyst exhibits the highest selectivity for C1 products (>80%). The phase-separated CuPd and Cu3Pd achieve higher selectivity (>60%) for C2 chemicals than CuPd3 and ordered CuPd, which suggests that the probability of dimerization of C1 intermediates is higher on surfaces with neighboring Cu atoms. Based on surface valence band spectra, geometric effects rather than electronic effects seem to be key in determining the selectivity of bimetallic Cu–Pd catalysts. These results imply that selectivities to different products can be tuned by geometric arrangements. This insight may benefit the design of catalytic surfaces that further improve activity and selectivity for CO₂ reduction