Nanosheet-state cobalt-manganese oxide with multifarious active regions derived from oxidation-etching of metal organic framework precursor for catalytic combustion of toluene.

For the first time, a nanosheet-state CoMnx mixed oxide with multifarious active regions was synthesized by oxidation-etching assembly of metal organic framework (MOF) precursor and applied for catalytic combustion of toluene at low temperatures. The obtained optimum catalyst denoted as CoMn6 showed excellent performance, which achieved 90% conversion of 1,000 ppm toluene under a weight hourly space velocity (WHSV) of 60,000 mL/(g·h) at 219 °C. While, it also exhibited long-term stability with strong water resistance property. The characterizations of physicochemical properties indicated that the oxidation-etching assembly process built an abundant mesoporous structure in the CoMnx catalyst, which greatly increased the specific surface area (SSA). Especially, potassium permanganate as oxidant and manganese source led to uniform dispersion and assembling of cobalt atoms, which caused the generation of low-crystallinity CoMnx mixed oxide with abundant dislocations, vacancies, phase interfaces and amorphous structures, resulting in excellent low-temperature reducibility, outstanding lattice oxygen mobility and abundant active species such as Mn3+, Co3+ and adsorbed oxygen species. Density functional theory (DFT) calculations demonstrated that gaseous oxygen with the longer bond length (1.406 Å) and stronger adsorption energy (-4.443 eV) could be adsorbed and activated well on the MnCo2O4.5 (311) plane, which is beneficial for the toluene oxidation. In situ diffuse reflectance infrared spectroscopy (DRIFTS) technique was applied to track the intermediates of toluene combustion under different atmospheres, which further deduced the contributions of different active regions and oxidation mechanism over the CoMnx catalyst. The present facile strategy of oxidation-etching assembly of the MOF precursor for the creating of novel catalyst with high performance could be applied in a wide variety of materials besides VOC combustion catalysts.

Microwave-assisted synthesis of manganese oxide catalysts for total toluene oxidation.

Oxygen vacancy on the heterogeneous catalyst is of great importance to the catalysis of volatile organic compound (VOC) oxidation. Herein, microwave radiation with special energy-excitation is successfully utilized for the post-processing of a series of manganese oxides (MnOx) to generate oxygen vacancies. It is found that the MnOx catalyst with 60 min of microwave radiation demonstrates higher activity for toluene oxidation with a T50% of 210 °C and a T100% of 223 °C, which is attributed to the higher concentration of oxygen vacancies derived from the rich phase interface defects resulted from the microwave radiation. Furthermore, the Mn-MW-60 catalyst possesses excellent thermal stability and water vapor tolerance even under 20 vol% H2O atmospheres within 60 h. In situ DRIFTS analysis verifies that both surface and lattice oxygen species simultaneously participate the oxidation process, and all reactions over different environments follows two different pathways. Meanwhile, it is proposed that those oxygen vacancies derived from microwave radiation could facilitate the rate-controlling step of opening the aromatic ring based on the electron back-donation, thereby leading to the increment of catalytic activity.

Trace holmium assisting delaminated OMS-2 catalysts for total toluene oxidation at low temperature.

In this study, octahedral molecular sieve (OMS-2) is successfully delaminated by using trace holmium (Ho) via a facile redox co-precipitation route, which exhibits high performance for the total toluene oxidation at low temperature. High resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) analyses verify that abundant multi-phase interfaces and lattice dislocations are formed on the obtained delaminated OMS-2 by the Ho (Ho-OMS-2), which can induce more active oxygen species. In particular, the delaminated OMS-2 with a trace Ho amount has a high Oads/Olatt ratio with a balanced ratio of Mn3+ and Mn4+, demonstrating much higher activity (T100% of 228 °C even under 5 vol% H2O vapor over 0.5% Ho-OMS-2) than the parent OMS-2 (T100% of 261 °C) for the total toluene oxidation. Furthermore, the positive effect of the introduction of H2O on catalytic activity, especially the enhancement of the conversion of intermediates into CO2 and H2O, is verified by the in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). Based on these results, the reaction mechanism for toluene oxidation over the OMS-2 based catalyst is proposed. It is expected to provide an effective preparation method to obtain high-performance catalysts for the VOCs oxidation at low temperatures.

The catalytic oxidation performance of toluene over the Ce-Mn-Ox catalysts: Effect of synthetic routes.

Ce-Mn-Ox catalysts were synthesized by impregnation (CM-IM), co-precipitation (CM-CP), citrate sol-gel (CM-SG) and hydrothermal (CM-HT) methods. The synthesis methods exhibited a great impact on the physicochemical properties of catalysts, resulting in different catalytic activity. The catalytic oxidation activity of toluene followed the sequence: CM-HT (T50: 234 °C; T90: 246 °C) > CM-SG (T50: 242 °C; T90: 249 °C) > CM-CP (T50: 243 °C; T90: 259 °C) > CM-IM (T50: 251 °C; T90: 261 °C), which was consistent with the sequence of surface relative percentage of Cov, Ce3+, Mn3+, Oα and r values. Among them, CM-HT showed the best catalytic oxidation performance of toluene due to more structural defects, oxygen vacancies, surface adsorption oxygen, normalized conversion rate and other active species. In addition, CM-HT catalysts showed reliable water resistance and good durability, implying the potential industrial application.

Mechanism of thermal phase transition of a ferroelectric liquid crystal with monotropic transition temperature studied by infrared spectroscopy combined with principal component analysis and sample-sample two-dimensional correlation spectroscopy.

Infrared (IR) spectra of FLC-154 (FLC: ferroelectric liquid crystal) with monotropic phase transition under a nonalignment state with a sample layer thickness of 24.5 microm were measured for heating process from 55 to 90 degrees C and a cooling process from 90 to 55 degrees C in increments of 1 degrees C. The thermal dynamics of FLC-154 were investigated by use of IR spectroscopy combined with principal component analysis (PCA) and sample-sample two-dimensional (2D) correlation spectroscopy. During the cooling, the FLC-154 molecule passes through the monotropic smectic-C* (Sm-C*) phase, which is transformed from the Sm-A phase. The results from PCA suggest that during the heating process, the thermal dynamics of the alkyl chains, core moiety, and C=O groups are similar to each other. Furthermore, PCA and sample-sample 2D correlation spectroscopy indicate that the alkyl chains and C=O groups in the chiral and core moieties are responsible for the emergence of the Sm-C* phase. This conclusion is very important because the IR data have given more evident cause for the emergence of the Sm-C* phase than the theoretical models such as the molecular-statistical theory of ferroelectric ordering and the indigenous polarization theory. Moreover, it has been found that some of the trans conformations of the alkyl chains of FLC-154 change partly to the gauche conformation when the phase transition from the crystalline phase to the Sm-A phase occurs. It has also been found that the intermolecular interactions of the C=O group in the core moiety in the Sm-A phase are weaker than those in the crystalline phase and that the conformational change occurs on the C-O-C bonds in the core moiety upon going from the crystalline to the Sm-A phase.

Dynamics of a ferroelectric liquid crystal with a naphthalene ring during electric-field-induced switching studied by time-resolved infrared spectroscopy combined with two-dimensional correlation spectroscopy.

The dynamics of a ferroelectric liquid crystal with a naphthalene ring (FLC-3) during the electric-field-induced switching between two surface-stabilized ferroelectric liquid crystal states were investigated by time-resolved infrared (IR) spectroscopy combined with two-dimensional (2D) correlation spectroscopy. Time-resolved IR spectra of FLC-3 in a planar-aligned cell were measured as a function of the polarization angle range from 0 degree to 180 degrees under a rectangular electric field of +/- 40 V with a 5 kHz frequency in the smectic-C* (Sm-C*) phase at 137 degrees C. From these spectra we explore details about the reorientation process of the alkyl chains, the core, and the large C=O dipole moments of FLC-3 at all the delay times. The 2D correlation spectroscopy was applied to the polarization-angle-dependent spectra for different delay times and to the time-resolved spectra at certain polarization angles to reveal the relative orientation of the C=O groups and the core moiety during the electric-field-induced switching. It was found from the present study that the relative orientation of the C=O groups and the core remains unchanged during the initial period of the reorientation, while it is reversed at a certain moment and then kept unchanged again. Moreover, the alkyl chains, C=O groups, and core moieties posses different dynamics during the fast course of electric-field-induced switching by analyzing time-resolved spectra.