Raman Scattering Spectra of Boron Imidazolate Frameworks Containing Paramagnetic Ions

We present a Raman scattering spectroscopic study of boron imidazolate metal-organic frameworks (BIFs) with a number of paramagnetic ions in a wide frequency range from 25 to 1700 cm$^{-1}$, which covers local vibrations of the linkers and well as collective lattice vibrations. We show that the spectral region above 800 cm$^{-1}$ belongs to the local vibrations of the linkers, which have the same frequencies for the studied BIFs without any dependence on the structure of the BIFs, and are easily interpreted based on the spectra of imidazolate linkers. In contrast, collective lattice vibrations, observed below 100 cm$^{-1}$, show a distinction between cage and two-dimensional BIFs structures, with a weak dependence on the metal node. We identify the range of vibrations around 200 cm$^{-1}$, which are distinct for each MOF, depending on a metal node. Our work demonstrates the energy hierarchy in the vibrational response of BIFs

Platinum-decorated carbon nanotubes for hydrogen oxidation and proton reduction in solid acid electrochemical cells

Pt-decorated carbon nanotubes (Pt-CNTs) were used to enhance proton reduction and hydrogen evolution in solid acid electrochemical cells based on the proton-conducting electrolyte CsH_2PO_4. The carbon nanotubes served as interconnects to the current collector and as a platform for interaction between the Pt and CsH_2PO_4, ensuring minimal catalyst isolation and a large number density of active sites. Particle size matching was achieved by using electrospray deposition to form sub-micron to nanometric CsH_2PO_4. A porous composite electrode was fabricated from electrospray deposition of a solution of Pt-CNTs and CsH_2PO_4. Using AC impedance spectroscopy and cyclic voltammetry, the total electrode overpotential corresponding to proton reduction and hydrogen oxidation of the most active electrodes containing just 0.014 mg cm^(−1) of Pt was found to be 0.1 V (or 0.05 V per electrode) at a current density of 42 mA cm^(−2) for a measurement temperature of 240 °C and a hydrogen-steam atmosphere. The zero bias electrode impedance was 1.2 Ω cm2, corresponding to a Pt utilization of 61 S mg^(−1), a 3-fold improvement over state-of-the-art electrodes with a 50× decrease in Pt loading

Carbon Dioxide Utilisation -The Formate Route

UIDB/50006/2020 CEEC-Individual 2017 Program Contract.The relentless rise of atmospheric CO2 is causing large and unpredictable impacts on the Earth climate, due to the CO2 significant greenhouse effect, besides being responsible for the ocean acidification, with consequent huge impacts in our daily lives and in all forms of life. To stop spiral of destruction, we must actively reduce the CO2 emissions and develop new and more efficient “CO2 sinks”. We should be focused on the opportunities provided by exploiting this novel and huge carbon feedstock to produce de novo fuels and added-value compounds. The conversion of CO2 into formate offers key advantages for carbon recycling, and formate dehydrogenase (FDH) enzymes are at the centre of intense research, due to the “green” advantages the bioconversion can offer, namely substrate and product selectivity and specificity, in reactions run at ambient temperature and pressure and neutral pH. In this chapter, we describe the remarkable recent progress towards efficient and selective FDH-catalysed CO2 reduction to formate. We focus on the enzymes, discussing their structure and mechanism of action. Selected promising studies and successful proof of concepts of FDH-dependent CO2 reduction to formate and beyond are discussed, to highlight the power of FDHs and the challenges this CO2 bioconversion still faces.publishersversionpublishe

THE EXPERIMENTAL ANALYSIS OF BUBBLEDECK SLAB USING MODIFIED ELLIPTICAL BALLS

The Thirteenth East Asia-Pacific Conference on Structural Engineering and Construction (EASEC-13), September 11-13, 2013, Sapporo, Japan

Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions †

Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products

Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions.

Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products