A Comprehensive Pyrolysis Mechanism of Binuclear Chromium-Based Complexes for Superior OER Activity.

Transition metal oxides are widely pursued as potent electrocatalysts for the oxygen evolution reaction (OER). However, single-metal chromium catalysts remain underexplored due to their intrinsic activity limitations. Herein, we successfully synthesize mixed-valence, nitrogen-doped Cr2O3/CrO3/CrN@NC nanoelectrocatalysts via one-step targeted pyrolysis techniques from a binuclear Cr-based complex (Cr2(Salophen)2(CH3OH)2), which is strategically designed as a precursor. Comprehensive pyrolysis mechanisms were thoroughly delineated by using coupled thermogravimetric analysis and mass spectrometry (TG-MS) alongside X-ray diffraction. Below 800 °C, the generation of a reducing atmosphere was noted, while continuous pyrolysis at temperatures exceeding 800 °C promoted highly oxidized CrO3 species with an elevated +6 oxidation state. The optimized catalyst pyrolyzed at 1000 °C (Cr2O3/CrO3/CrN@NCs-1000) demonstrated remarkable OER activity with a low overpotential of 290 mV in 1 M KOH and excellent stability. Further density functional theory (DFT) calculations revealed a much smaller reaction energy barrier of CrO3 than the low oxidation state species for OER reactivity. This work reveals fresh strategies for rationally engineering chromium-based electrocatalysts and overcoming intrinsic roadblocks to enable efficient OER catalysis through a deliberate oxidation state and compositional tuning.

Mold-Free Manufacturing of Highly Sensitive and Fast-Response Pressure Sensors Through High-Resolution 3D Printing and Conformal Oxidative Chemical Vapor Deposition Polymers.

A new manufacturing paradigm is showcased to exclude conventional mold-dependent manufacturing of pressure sensors, which typically requires a series of complex and expensive patterning processes. This mold-free manufacturing leverages high-resolution 3D-printed multiscale microstructures as the substrate and a gas-phase conformal polymer coating technique to complete the mold-free sensing platform. The array of dome and spike structures with a controlled spike density of a 3D-printed substrate ensures a large contact surface with pressures applied and extended linearity in a wider pressure range. For uniform coating of sensing elements on the microstructured surface, oxidative chemical vapor deposition is employed to deposit a highly conformal and conductive sensing element, poly(3,4-ethylenedioxythiophene) at low temperatures (<60 °C). The fabricated pressure sensor reacts sensitively to various ranges of pressures (up to 185 kPa-1 ) depending on the density of the multiscale features and shows an ultrafast response time (≈36 µs). The mechanism investigations through the finite element analysis identify the effect of the multiscale structure on the figure-of-merit sensing performance. These unique findings are expected to be of significant relevance to technology that requires higher sensing capability, scalability, and facile adjustment of a sensor geometry in a cost-effective manufacturing manner.

Evaluation of immature granulocyte parameters in myeloid neoplasms assayed by Sysmex XN hematology analyzer.

Immature granulocytes (IGs) have significance for the diagnosis of myeloid neoplasms (MNs). The current study aims to use a hematology analyzer to evaluate the accuracy of IG parameters in MNs. Blood specimens from 388 patients with MN, 524 with non-hematological neoplasms (non-HNs), including 109 patients with inflammation and 68 undergoing G-CSF administration, and 500 healthy control subjects were analyzed. IG parameters was assayed by Sysmex XN-9000 (XN) and compared with manual assessments. A high level of agreement between IG% derived from XN and manual measurements for MN patients (r = 0.828, p < 0.0001) was revealed but only a moderate correlation for acute myeloid leukemia patients (AML; r = 0.597; p < 0.0001). Bland-Altman bias analysis was conducted, and the results showed that differences in IG% from XN and manual analysis for MN patients were considered clinically insignificant. ROC analysis demonstrated a good performance of IG# (AUC = 0.842) and IG% (AUC = 0.885) assessed by XN for MN patients with cut-off values of 0.200 × 109/L and 1.95%, respectively. IG parameters from Sysmex XN analyzer are helpful for screening of MNs even though granulocyte morphological abnormalities may interfere with IG parameter accuracy.

MnO2-decorated N-doped carbon nanotube with boosted activity for low-temperature oxidation of formaldehyde.

Low-temperature oxidative degradation of formaldehyde (HCHO) using non-noble metal catalysts is challenging. Herein, novel manganese dioxide (MnO2)/N-doped carbon nanotubes (NCNT) composites were prepared with varying MnO2 content. The surface properties and morphologies were analyzed using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM). Comparing with MnO2/carbon nanotubes (CNTs) catalyst, the 40% MnO2/NCNT exhibited much better activity and selectivity for HCHO oxidation, mineralizing 95% of HCHO (at 100 ppm) into CO2 at 30 °C at a gas hourly space velocity (GHSV) of 30,000 mL h-1  g-1. Density functional theory (DFT) calculation was used to analyze the difference in the catalytic activity of MnO2 with CNTs and NCNT carrier. It was confirmed that the oxygen on NCNT was more active than CNTs, which facilitated the regeneration of MnO2. This resulted in remarkably boosted activity for HCHO oxidation. The present work thus exploited an inexpensive approach to enhance the catalytic activity of transition metal oxides via depositing them on a suitable support.

Mechanistic insight into the catalytic oxidation of cyclohexane over carbon nanotubes: kinetic and in situ spectroscopic evidence.

As some of the most interesting metal-free catalysts, carbon nanotubes (CNTs) and other carbon-based nanomaterials show great promise for some important chemical reactions, such as the selective oxidation of cyclohexane (C6H12). Due to the lack of fundamental understanding of carbon catalysis in liquid-phase reactions, we have sought to unravel the role of CNTs in the catalytic oxidation of C6H12 through a combination of kinetic analysis, in situ spectroscopy, and density functional theory. The catalytic effect of CNTs originates from a weak interaction between radicals and their graphene skeletons, which confines the radicals around their surfaces. This, in turn, enhances the electron-transfer catalysis of peroxides to yield the corresponding alcohol and ketone.

Confined iron nanowires enhance the catalytic activity of carbon nanotubes in the aerobic oxidation of cyclohexane.

Inside job: New applications of carbon materials pave the way towards greener chemical syntheses. The encapsulation of metallic Fe within CNTs improves electron transfer between the metal and the CNTs. The resulting material offers a high catalytic activity and easy magnetic separation of catalyst in the heterogeneous selective oxidation of cyclohexane.