Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO4-Sepiolite Supports

In this work, the covalent immobilization of two ruthenium(II) complexes, i.e., [RuIICl (bpea){(S)(-)(BINAP)}](BF4), 1, and [RuIICl(bpea)(DPPE)](BF4), 2, where BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO4-Sepiolite@1 and AlPO4-Sepiolite@2) by using a N-tridentate ligand N,N-bis-(2-pyridylmethyl)ethylamine (bpea), linked to an amorphous AlPO4-Sepiolite (20/80) inorganic support. This AlPO4-sepiolite support is able to immobilize the double amount of ruthenium complex (1.65%) than the amorphous AlPO4 (0.89%). Both heterogenized complexes have been assessed as catalysts in the liquid phase hydrogenation of several substrates with carbonyl and/or olefinic double bonds using methanol as solvent, attaining good catalytic activity and high enantioselectivity (99%). The highest Turn Over Number (TON) value (748.6) was obtained over the [RuII Cl (bpea)(DPPE)](BF4) 2 catalyst, although the [RuIICl(bpea){(S)(-)(BINAP)}](BF4) 1 exhibits better reusability. In fact, the [RuIICl(bpea){(S)(-)(BINAP)}](BF4) immobilized on AlPO4-Sepiolite maintained the activity throughout 14 successive runs. Furthermore, some findings on hydrogenation mechanisms of the α,β-unsaturated carbonyl compounds over Ru catalysts have been also obtained.

Phosphate Sorption Speciation and Precipitation Mechanisms on Amorphous Aluminum Hydroxide

Aluminum (Al) oxides are important adsorbents for phosphate in soils and sediments, and significantly limit Phosphate (P) mobility and bioavailability, but the speciation of surface-adsorbed phosphate on Al oxides remains poorly understood. Here, phosphate sorption speciation on amorphous Al hydroxide (AAH) was determined under pH 3–8 and P concentration of 0.03 mM–15 mM using various spectroscopic approaches, and phosphate precipitation mechanisms were discussed as well. AAH exhibits an extremely high phosphate sorption capacity, increasing from 3.80 mmol/g at pH 7 to 4.63 mmol/g at pH 3. Regardless of reaction pH, with increasing P sorption loading, the sorption mechanism transits from bidentate binuclear (BB) surface complexation with dP-Al of 3.12 Å to surface precipitation of analogous amorphous AlPO4 (AAP), possibly with ternary complexes, such as (≡Al-O)2-PO2-Al, as intermediate products. Additionally, the percentage of precipitated phosphate occurring in AAP linearly and positively correlates with P sorption loading. Compared to phosphate reaction with ferrihydrite, phosphate adsorbs and precipitates more readily on AAH due to the higher solubility product (Ksp) of AAH. The formation of AAP particles involves AlIII release, which is promoted by phosphate adsorption, and its subsequent precipitation with phosphate at AAH surfaces or in the bulk solution.

Synthesis and study of magnetic properties of high temperature stable Ni nanoparticles in a nearly amorphous AlPO4 matrix in an oxidative atmosphere

Graphitized carbon coated Ni nanoparticles were synthesized in an AlPO4 matrix in situ in an oxidative atmosphere without using any foreign reducing agent.