Cu⁰and Pd⁰loaded Organo-Bentonites as Sponge-like Matrices for Hydrogen Reversible Capture at Ambient Conditions

Abstract

Sponge-like gluco-and thioglycerol-organo-bentonite hosting Cu 0 and Pd 0 subnanoparticles with high affinity towards hydrogen were synthesized through an unprecedented procedure involving a chemical grafting of (3-azidopropyl)triethoxysilane, followed by Cu-catalyzed azide-alkyne cycloaddition with propargyl glucoside or triallyl propargyl pentaerythritol. Further, thioglycerol groups were attached to the alkene groups by photolysis (TEC reaction). This resulted in a structure swelling, but further Cu 0 or Pd 0 nanoparticle incorporation produced a compaction due to strong O:metal and S:metal interactions that improve metal stabilization and prevent re-aggregation. Such a structure favored hydrogen capture via physical condensation with easy release at nearly ambient temperature at the expense of hydrogen dissolution in the metal bulk. This innovative concept opens new prospects for obtaining low cost clay-based matrices for a truly reversible capture of hydrogen.[a] Dr.

Metal-inorganic-organic core–shell material as efficient matrices for CO2 adsorption: Synthesis, properties and kinetic studies

“…The marked depletion of the 3400 cm −1 after APTES grafting indicates the occurrence of HC -O-Si-propyl bridges. The total disappearance of the 2919 cm −1 band related to the asymmetric stretching vibration of CH 2 and C -H aliphatic groups after Cu 0 incorporation must be due to the occurrence of strong Cu: OH-and Cu:N-interactions that induce a compaction of the organic entanglement around CuNPs, in agreement with our previous statements [35,36] . Incorporation of CuNPs also induced a marked shift of the 1065 cm −1 band towards lower wavenumber ( Fig.…”

“…Cu 0 particle insertion induced marked decay of the specific surface area and average pore volume down to 20 m 2 /g and 0.12 nm, respectively, thereby confirming our previously stated structure compaction. This phenomenon is a special feature of the occurrence of -N:Metal and -O:Metal Lewis-Acid-Base (LAB) interactions, as already reported elsewhere [14,36,[40][41][42][43] .…”

“…4 ), suggesting a N -C bond weakening by the appearance of strong Cu 0 :N-propyl interaction. Terminal OH groups should also contribute to this compaction of the organic entanglement via Cu 0 : OH-Lewis-acid-base interactions with a possible synergy between the N and O atoms in CuNP stabilization, as supported by the slight intensity decrease of the 330 0-360 0 cm −1 bands [36,37] .…”

“…It turned out to act as host matrice for copper-zero dispersion and as effective adsorbent for CO 2 at room temperature like other materials with attenuated basicity [15] . The specific surface area was not an essential requirement, inasmuch as compacted matrices paradoxically displayed higher affinity towards CO 2 than much more expanded and more porous materials [14,36,37] . Hence, a new strategy was rather focused on the preparation of compacted matrices that promote metal stabilization and attenuate CO 2 retention strength.…”

Dendrimers: syntheses, toxicity, and applications toward catalysis, environmental sciences, and nanomedecine

“…[8][9][10][11][12][13][14][15][16][17] The intrinsic properties of the dendritic organic moiety 10,[18][19][20] are designed according to the targeted applications [21][22][23][24] or to confer specific features to the hybrid materials when supported on inorganic supports. [25][26][27][28][29][30][31][32][33][34] In the area including energy and green chemistry, recently, major advances have been made in this regard by synthesizing metalorgano-aluminosilicates through in-situ synthesis of metal nanoparticles within the entanglements of supported dendrimers. 35 The development of the new concept of "Truly Reversible Gas Capture" by clay-dendrimer based adsorbents that do not need thermal regeneration has particularly attracted attention.…”