2D Solid-State HETCOR 1H-13C NMR Experiments with Variable Cross Polarization Times as a Tool for a Better Understanding of the Chemistry of Cellulose-Based Pyrochars—A Tutorial

The chemistry and nature of biochars are still far from being well understood. In the present work, solid-state 2D HETCOR 1H-13C NMR spectroscopy is introduced for an improved characterization of the aromatic network in biochars. To that end, a pyrochar obtained from the pyrolysis of cellulose at 350 °C for 1 h was used as an example. Variation of the contact time during cross polarization from 50 µs, to 200 µs and 1000 µs gave information about the protonation degree of the different C groups and their interactions. We demonstrated that carbohydrates did not survive the used pyrolysis conditions. Therefore, O-alkyl C was assigned to ethers. Phenols were not identified to a higher extent suggesting that furan and benzofuran-type units determine the O-functionality of the aromatic domains. The latter are directly connected to alkyl chains. Those features are expected to affect chemical but also physical properties of the biochar. Based on our results, we developed a new concept describing the nature of the aromatic network in the studied cellulose-based pyrochars. The latter contrasts common views about the chemical nature of biochar, possibly because pyrolysis temperatures > 350 °C are required for achieving advanced condensation of the aromatic domains.

Unusual temperature-sensitive protonation behaviour of 4-(dimethylamino)pyridine

An unusually strong impact of temperature on the protonation degree of DMAP in strong acid solutions has been found.

Dynamics and Rheological Behavior of Chitosan-Grafted-Polyacrylamide in Aqueous Solution upon Heating

In this work, the transformation of chitosan-grafted-polyacrylamide (GPAM) aggregates in aqueous solution upon heating was explored by cryo-electron microscope (cryo-TEM) and dynamic light scattering (DLS), and larger aggregates were formed in GPAM aqueous solution upon heating, which were responsible for the thermo-thickening behavior of GPAM aqueous solution during the heating process. The heating initiates a transformation from H-bonding aggregates to a large-sized cluster formed by self-assembled hydrophobic chitosan backbones. The acetic acid (HAc) concentration has a significant effect on the thermo-thickening behavior of GPAM aqueous solution; there is a critical value of the concentration (>0.005 M) for the thermo-thickening of 10 mg/mL GPAM solution. The concentration of HAc will affect the protonation degree of GPAM, and affect the strength of the electrostatic repulsion between GPAM molecular segments, which will have a significant effect on the state of the aggregates in solution. Other factors that have an influence on the thermo-thickening behavior of GPAM aqueous solution upon heating were investigated and discussed in detail, including the heating rate and shear rate.

Proton conduction studies on four porous and nonporous coordination polymers with different acidities and water uptake

Acidity and water absorption ability are important influencing factors on proton conducting behavior, which are determined by the protonation degree and amount of hydrophilic groups in the crystal structures, respectively.

Protonation-induced molecular permeation at the oil/water interface in an electric field

The relationship between the protonation degree increment and applied voltage was proposed as a guide for controlling the protonation via applying an electric field.

Protonation and Photocatalytic Activity of the Rb2La2Ti3O10 Layered Oxide in the Reaction of Hydrogen Production

The Rb2La2Ti3O10 layered oxide was synthesized by the solid-state method. Three phases with different protonation degrees and intercalated water contents were obtained from the initial compound by the treatment with distilled water and hydrochloric acid. The obtained samples were characterized by powder X-ray diffraction, SEM, X-ray microanalysis, BET, DRS, and TG. It was found that the complete ion exchange of Rb+ for H+ in the layered oxide Rb2La2Ti3O10 proceeds through the formation of two metastable intermediate phases with average protonation degrees of 0.5 and 0.75, which successively transform from one to another. Each of these phase transformations is accompanied not only by the contraction of the interlayer distance but also by the displacement of adjacent perovskite layers by 1/2 of the cell parameter which results in the change in the space group. The photocatalytic activity of obtained samples decreases with the increase in the protonation degree, which correlates with the decrease in the intercalated water content.

2nd coordination sphere controlled electron transfer of iron hangman complexes on electrodes probed by surface enhanced vibrational spectroscopy

Surface enhanced vibrational spectroscopy shows the correlation between electron transfer kinetics and protonation degree of Fe Hangman complexes on electrodes.

Protonation Degree of Doped Polyaniline with Sulfosalicylic Acid as Function of the Synthetic Method

X-ray photoelectron spectroscopy (XPS) has been employed to investigate the protonation degree of polyaniline doped with sulfosalicylic acid (PAni-SSA) obtained by different synthetic methods. The protonation degree has been compared to electrical conductivity. Prepared PAni-SSA through the redoping process in an agate mortar displays conductivity values within the range of 1S/cm. Protonation degree of synthesized PAni-SSA by aqueous dispersion polymerization of aniline in the presence of SSA is higher than 50 %, indicating that a substantial portion of amine units have also been protonated. The C/N and S/N molar ratios obtained by XPS analysis indicate that the polyaniline chains obtained by aqueous dispersion polymerization are protonated by both sulfate anions.