Assessing CO2 Capture in Porous Sorbents via Solid-State NMR-Assisted Adsorption Techniques.

Adsorption isotherms obtained through volumetric measurements are widely used to estimate the gas adsorption performance of porous materials. Nonetheless, there is always ambiguity regarding the contributions of chemi- and physisorption processes to the overall retained gas volume. In this work, we propose, for the first time, the use of solid-state NMR (ssNMR) to generate isotherms of CO2 adsorbed onto an amine-modified silica sorbent. This method enables the separation of six individual isotherms for chemi- and physisorbed CO2 components, a feat only possible using the discrimination power of NMR spectroscopy. The adsorption mechanism for each adsorbed species was ascertained by tracking their adsorption profiles at various pressures. The proposed method was validated against conventional volumetric adsorption measurements. The isotherm curves obtained by the proposed ssNMR-assisted approach enable advanced analysis of the sorbents, revealing the potential of variable-pressure NMR experiments in gas adsorption applications.

Water-Soluble Polymeric Carbon Nitride Colloidal Nanoparticles for Highly Selective Quasi-Homogeneous Photocatalysis.

Heptazine-based polymeric carbon nitrides (PCN) are promising photocatalysts for light-driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom-up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi-homogeneous conditions. The superior performance of water-soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H2 O2 production via reduction of oxygen accompanied by highly selective photooxidation of 4-methoxybenzyl alcohol and benzyl alcohol or lignocellulose-derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re-dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.

Unravelling the structure of CO2 in silica adsorbents: an NMR and computational perspective.

This comprehensive review describes recent advancements in the use of solid-state NMR-assisted methods and computational modeling strategies to unravel gas adsorption mechanisms and CO2 speciation in porous CO2-adsorbent silica materials at the atomic scale. This work provides new perspectives for the innovative modifications of these materials rendering them more amenable to the use of advanced NMR methods.

Valorization of Crab Shells as Potential Sorbent Materials for CO2 Capture.

This study delves into the potential advantage of utilizing crab shells as sustainable solid adsorbents for CO2 capture, offering an environmentally friendly alternative to conventional porous adsorbents, such as zeolites, silicas, metal-organic frameworks (MOFs), and porous carbons. The investigation focuses on crab shell waste, which exhibits inherent natural porosity and N-bearing groups, making them promising candidates for CO2 physisorption and chemisorption applications. Selective deproteinization and demineralization treatments were used to enhance textural properties while preserving the natural porous structure of the crab shells. The impact of deproteinization and demineralization treatments on CO2 adsorption and speciation at the atomic scale, via solid-state NMR, and correlated findings with textural properties and biomass composition were investigated. The best-performing sample exhibits a surface area of 36 m2/g and a CO2 adsorption capacity of 0.31 mmol/g at 1 bar and 298 K, representing gains of ∼3.5 and 2, respectively, compared to the pristine crab shell. These results underline the potential of fishing industry wastes as a cost-effective, renewable, and eco-friendly source to produce functional porous adsorbents.

"Hidden" CO2 in Amine-Modified Porous Silicas Enables Full Quantitative NMR Identification of Physi- and Chemisorbed CO2 Species.

Although spectroscopic investigation of surface chemisorbed CO2 species has been the focus of most studies, identifying different domains of weakly interacting (physisorbed) CO2 molecules in confined spaces is less trivial as they are often indistinguishable resorting to (isotropic) NMR chemical shift or vibrational band analyses. Herein, we undertake for the first time a thorough solid-state NMR analysis of CO2 species physisorbed prior to and after amine-functionalization of silica surfaces; combining 13C NMR chemical shift anisotropy (CSA) and longitudinal relaxation times (T 1). These methods were used to quantitatively distinguish otherwise overlapping physisorbed CO2 signals, which contributed to an empirical model of CO2 speciation for the physi- and chemisorbed fractions. The quantitatively measured T 1 values confirm the presence of CO2 molecular dynamics on the microsecond, millisecond, and second time scales, strongly supporting the existence of up to three physisorbed CO2 species with proportions of about 15%, 15%, and 70%, respectively. Our approach takes advantage from using adsorbed 13C-labeled CO2 as probe molecules and quantitative cross-polarization magic-angle spinning to study both physi- and chemisorbed CO2 species, showing that 45% of chemisorbed CO2 versus 55% of physisorbed CO2 is formed from the overall confined CO2 in amine-modified hybrid silicas. A total of six distinct CO2 environments were identified from which three physisorbed CO2 were discriminated, coined here as "gas, liquid, and solid-like" CO2 species. The complex nature of physisorbed CO2 in the presence and absence of chemisorbed CO2 species is revealed, shedding light on what fractions of weakly interacting CO2 are affected upon pore functionalization. This work extends the current knowledge on CO2 sorption mechanisms providing new clues toward CO2 sorbent optimization.

Photocatalytic degradation of 2-(4-methylphenoxy)ethanol over TiO2 spheres.

The photocatalytic TiO2-assisted decomposition of 2-(4-methylphenoxy)ethanol (MPET) in aqueous solution has been studied for the first time. The intermediate compounds of MPET photodegradation have been also determined. A toxic p-cresol is formed in significant quantities during the photocatalytic reaction. A solvent-exchange approach for a template-free preparation of spherical TiO2 particles has been described, which is based solely on precipitation of hydrous titania from aqueous titanium peroxo complex by using organic solvents. The proposed method favours the formation of spherical titania particles with a mean size varying from 50 to 260nm depending on the choice of solvent. The procedure for converting nonporous titania spheres into mesoporous material maintaining the same spherical morphology has been developed. The synthesized TiO2 spheres demonstrate a degree of MPET photo-degradation close to that of the commercial titania Aeroxide P25, besides being successfully recovered and reused for four reaction cycles without loss of photocatalytic activity. The effectiveness of the commercial Aeroxide P25 in MPET photodegradation, on the other hand, suffers 10-time drop during the third reaction cycle, which is attributed to its poor recoverability because the photocatalyst is composed of small particles of 20nm size.

A hydrothermal peroxo method for preparation of highly crystalline silica-titania photocatalysts.

A new completely inorganic method of preparation of silica-titania photocatalyst has been described. It has been established that the addition of silica promotes crystallinity of TiO2 anatase phase. Relative crystallinity and TiO2 crystal size in the silica-titania particles increase with the silica content until SiO2/TiO2 molar ratio of 0.9, but at higher molar ratios they start to decrease. The single-source precursor containing peroxo titanic (PTA) and silicic acids has been proved to be responsible for high crystallinity of TiO2 encapsulated into amorphous silica. It has been proposed that peroxo groups enhance rapid formation of crystalline titania seeds, while silica controls their growth. It has been concluded from the TEM that the most morphologically uniform anatase crystallites covered with SiO2 particles are prepared at SiO2/TiO2 molar ratio of 0.4. This sample, according to (29)Si NMR, also shows the high content of hydroxylated silica Q(3) and Q(2) groups, and it is the most photocatalytically active in UV-assisted decomposition of methylene blue among the tested materials. It has been determined that the increase in the amount of the condensed Q(4) silica in the mixed oxides leads to the decrease in photocatalytic performance of the material, despite its better crystallinity. High crystallinity, low degree of incorporation of Ti atoms in SiO2 in the mixed oxide and adsorption of methylene blue in the vicinity of photoactive sites on the hydroxylated silica have been considered as the main factors determining the high degradation degree of methylene blue in the presence of silica-titania.