Low-temperature Reaction Research Articles

Cyclometalated half‐sandwich iridium complexes: Synthesis, characterization, and catalytic activity in preparation of esters from halides by using formate as both CO source and coupling partner

A highly efficient carbonylation of aryl halides using half‐sandwich iridium catalysis was developed, providing a new avenue for synthesizing carboxylic ester derivatives and yielding consistently impressive results. These iridium complexes demonstrated remarkable catalytic performance in the coupling reaction using phenyl formate derivatives as the source of CO, phenol, and aryl halides as the starting material in the presence of air and possessed good air and moisture stability properties. Ester products with different substituents were synthesized at low reaction temperatures without the need for an inert atmosphere, leading to high yields. The broad substrate scope, impressive catalytic activity, and mild reaction conditions suggest promising industrial applications for this catalytic system. The desired metal complexes 1–4 have been well proven by attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR), nuclear magnetic resonance (NMR), and elemental analysis (EA). The molecular structure of the cyclometalated iridium complexes 2 and 3 was proven through X‐ray crystallography. Additionally, the possible mechanism of this Ir‐catalyzed process is further supported by the density functional theory (DFT) study.

In Situ Self-Assembly of Nitrogen-Doped 3D Flower-like Hierarchical Porous Carbon and Its Application for Supercapacitors.

The hierarchical porous carbon-based materials derived from biomass are beneficial for the enhancement of electrochemical performances in supercapacitors. Herein, we report the fabrication of nitrogen-doped 3D flower-like hierarchical porous carbon (NPC) assembled by nanosheets using a mixture of urea, ZnCl2, and starch via a low-temperature hydrothermal reaction and high-temperature carbonization process. As a consequence, the optimized mass ratio for the mixture is 2:2:2 and the temperature is 700 °C. The NPC structures are capable of electron transport and ion diffusion owing to their high specific surface area (1498.4 m2 g-1) and rich heteroatoms. Thereby, the resultant NPC electrodes display excellent capacitive performance, with a high specific capacitance of 249.7 F g-1 at 1.0 A g-1 and good cycling stability. Remarkably, this implies a superior energy density of 42.98 Wh kg-1 with a power density of 7500 W kg-1 in organic electrolyte for the symmetrical supercapacitor. This result verifies the good performance of as-synthesized carbon materials in capacitive energy storage applications, which is inseparable from the hierarchical porous features of the materials.

Pd‐Pt Bimetallic Catalysts for Enhanced Low‐Temperature Hydrodeoxygenation of Vanillin

AbstractTo make pyrolytic bio‐oil useful as a transportation fuel, the oxygen content must be reduced, and this can be carried out by using catalytic hydrodeoxygenation (HDO) reaction. The greatest challenge is associated with the removal of strongly bound oxygenated groups without saturating the aromatic ring while preserving the number of carbons. However, the development of a stable catalyst that can selectively remove such oxygenated groups with low hydrogen consumption is still challenging. In this context, a systematic study on HDO of vanillin on bimetallic Pd−Pt catalysts was carried out. It aims to study the effect of bimetallic synergy in terms of activity and selectivity to creosol. Metallic nanoparticles of Pd and Pt were synthesized by sol immobilization technique and deposited on TiO2. The conversion of vanillin was correlated to the Pd−Pt atomic ratio, while the production of the creosol was correlated to the Pd(0)/(Pd+Pt) ratio at the surface. Full conversion of vanillin was obtained at low reaction temperature (20 °C) achieving nearly 100 % selectivity to creosol. These results represent a step forward in advancing the development of more efficient and sustainable processes for bio‐oil upgrading.

Small iridium clusters supported on TiO2 as catalysts for intensifying low-temperature methane activation and reforming

Hydrogen production via low-temperature (<550 °C) steam reforming of methane (SRM) has attracted increasing research attention due to its importance as an alternative, efficient, and environmentally benign energy carrier. The thermodynamic limitation of low-temperature SRM can be eased by process design such as using a membrane reactor or an adsorption-enhanced reforming process, and an active low-temperature SRM catalyst with high stability would be indispensable. Herein, we report a 2 wt% Ir/TiO2 catalyst that exhibits high methane conversion activity in low-temperature SRM with a relatively high turnover frequency (TOF) and a low activation energy in comparison with the literature. Long-term catalyst stability test demonstrates a good resistance to coking and sintering during low-temperature SRM reactions. In situ spectroscopy analyses and density functional theory (DFT) calculations reveal that the small Ir clusters and Ir single atoms (SAs) are both active for methane conversion, while the clusters exhibit higher activity than SAs for low-temperature SRM reaction. Microkinetic simulation based on DFT calculations shows consistent product formation temperatures and the simulation nicely reproduces the product distribution observed in experimental analysis, which confirms the superior SRM activity of the TiO2-supported Ir clusters in this work.

Aspen Simulation Study of Dual-Fluidized Bed Biomass Gasification

This article establishes a thermodynamic model of a dual-fluidized bed biomass gasification process based on the Aspen Plus software platform and studies the operational control characteristics of the dual-fluidized bed. Firstly, the reliability of the model is verified by comparing it with the existing experimental data, and then the influence of different process parameters on the operation and gasification characteristics of the dual-fluidized bed system is investigated. The main parameters studied in the operational process include the fuel feed rate, steam/biomass ratio (S/B), air equivalent ratio (ER), and circulating bed material amount, etc. Their influence on the gasification product composition, reactor temperature, gas heat value (QV), gas production rate (GV), carbon conversion rate (ηc), and gasification efficiency (η) is investigated. The study finds that fuel feed rate and circulating bed material amount are positively correlated with QV, ηc, and η; ER is positively correlated with GV and ηc but negatively correlated with QV and η; S/B is positively correlated with GV, ηc, and η but negatively correlated with QV. The addition of CaO is beneficial for increasing QV. In actual operation, a lower reaction temperature in the gasification bed can be achieved by reducing the circulating bed material amount, and a larger temperature difference between the combustion furnace and the gasification furnace helps to further improve the quality of the gas. At the same time, GV, ηc, and η need to be considered to find the most optimized operating conditions for maximizing the benefits. The model simulation results agree well with the experimental data, providing a reference for the operation and design of dual-fluidized beds and chemical looping technology based on dual-fluidized beds.

Revealing the two distinctive roles of HY zeolite in enhancing the activity and durability of manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR

Recently, metal oxide-zeolite hybrid systems have shown promise in enhancing catalytic performance in low-temperature selective catalytic reduction (SCR), but not much is known as to mechanistic details. The purpose of this study is to examine fluctuations in low-temperature activity contingent upon the presence or absence of zeolite and to elucidate a dual functional mechanism of mixed zeolite in improving the catalytic performance of MnOx, which is closely related to inter-particle diffusion of nitrite and nitrate species from MnOx to zeolite. Firstly, strong Brønsted acid sites on zeolite demonstrate a significantly faster reduction of diffused nitrite species compared to Brønsted/Lewis acid sites on MnOx. More importantly, we discovered that zeolite prevents ammonium nitrate deposition by absorbing and decomposing diffused nitrate species from MnOx. Such distinct interaction between zeolite and both nitrite and nitrate species clarified here will be of great promise in designing future hybrid catalytic materials for low-temperature NH3-SCR reactions.

Molecular insight into the structural and mechanical properties of Ca-based geopolymers

Ca-based geopolymers are a principal product of introducing calcium into geopolymers. Analyzing Ca-based geopolymers structural and mechanical properties aids in optimizing mix design of geopolymers. In this paper, partially reacted low-polymerization and fully reacted high-polymerization models were constructed to examine the structural and mechanical properties of Ca-based geopolymers with varying calcium contents via molecular dynamics simulations. Results show that Ca-based geopolymers contain pentacoordinate aluminum and tricluster oxygen which is more brittle and makes the structure loose. In low-polymerization models, an increase in calcium content accelerates the polymerization rate by overcoming the low-temperature reaction barrier. However, calcium content hinders the formation of pentacoordinate aluminum, decreasing the final degree of polymerization, resulting in weakened mechanical properties. In high-polymerization models, increased calcium decreases tricluster oxygen content, resulting in improved mechanical properties. While the hydrolysis reaction reduces mechanical properties, the weakening effect of water is greater than the enhancing effect of calcium.

Automated synthesis of [89Zr]ZrCl4, [89Zr]ZrDFOSquaramide-bisPh(PSMA) and [89Zr]ZrDFOSquaramide-TATE

BackgroundAutomated [89Zr]Zr-radiolabeling processes have the potential to streamline the production of [89Zr]Zr-labelled PET imaging agents. Most radiolabeling protocols use [89Zr][Zr(ox)4]4− as the starting material and oxalate is removed after radiolabeling. In some instances, radiolabeling with [89Zr]ZrCl4 as starting material gives better radiochemical yields at lower reaction temperatures. In this work, a fully-automated process for production of [89Zr]ZrCl4 is reported and its use for the synthesis of [89Zr]ZrDFOSq-bisPhPSMA and [89Zr]ZrDFOSq-TATE.ResultsA simple automated process for the isolation of [89Zr]ZrCl4 by trapping [89Zr][Zr(ox)4]4− on a bicarbonate-activated strong anion exchange cartridge followed by elution with 0.1 M HCl in 1 M NaCl was developed. [89Zr]ZrCl4 was routinely recovered from [89Zr][Zr(ox)4]4− in > 95% yield in mildly acidic solution of 0.1 M HCl in 1 M NaCl using a fully-automated process. The [89Zr]ZrCl4 was neutralized with sodium acetate buffer (0.25 M) removing the requirement for cumbersome manual neutralization with strong base. The mixture of [89Zr]ZrCl4 was used for direct automated radiolabeling reactions to produce [89Zr]Zr-DFOSquaramide-bisPhPSMA and [89Zr]ZrDFOSquaramide-TATE in 80–90% over all RCY in > 95% RCP.ConclusionsThis method for the production of [89Zr]ZrCl4 does not require removal of HCl by evaporation making this process relatively fast and efficient. The fully automated procedures for the production of [89Zr]ZrCl4 and its use in radiolabeling are well suited to support the centralized and standardized manufacture of multiple dose preparations of zirconium-89 based radiopharmaceuticals.

Realization of new n = 3 and n = 4 Dion-Jacobson layered perovskite series with interlayer K+ ions and perovskite blocks stabilized by Pr3+ ions

The structural flexibility of the perovskite blocks in the Dion-Jacobson family of layered perovskite oxides has successfully resulted in the generation of KPrNan-2NbnO3n+1 and KPrCan-2Nb2Tin-2O3n+1 (n = 3, 4). The stabilization of K+ ions preferring a six coordination in the interlayer region is significant compared to the facile formation of layered perovskite oxides possessing bigger Rb+ or Cs+ ions with an eight coordination in the interlayer. The structure of the n = 3 members, KPrNaNb3O10 (S. G. Cmcm; a = 3.8858(1) Å, b = 29.6553(9) Å, c = 7.7635(3) Å) and KPrCaNb2TiO10 (S. G. Cmcm; a = 3.8634(2) Å, b = 29.4808(2) Å, c = 7.6945(5) Å) were confirmed respectively using the Rietveld and Le Bail methods utilizing the powder X-ray diffraction data. The n = 4 members, KPrNa2Nb4O13 and KPrCa2Nb2Ti2O13 are synthesized through high-temperature ceramic methods. The compounds are phase pure as confirmed from the X-ray diffraction data and were characterized by UV–visible diffuse reflectance measurements. These two-dimensional oxides also undergo facile topochemical ion-exchange and intercalation reactions and opens up several interesting possibilities. We have replaced the K+ ions in the interlayer by H+, Li+, Na+ ions and [CuCl]+ groups through low temperature reactions. The usefulness of various Dion-Jacobson layered perovskite oxides for potential photocatalytic applications has been explored by determining the optical band gaps, the valence band, and the conduction band energy levels based on the UV–visible diffuse reflectance measurements.

Effect of calcination temperature on the performance of K-Co/Al2O3 catalyst for oxidative coupling of methane

The oxidative coupling of methane (OCM) involves directly converting methane to C2+ hydrocarbons (such as ethylene and ethane) via a reaction with oxygen. This study elucidated the effect of the calcination temperature on the structure and catalytic performance of potassium-doped-cobalt oxide supported on an alumina (K-Co/Al2O3) catalyst for the OCM reaction. The catalyst was highly active at relatively low reactor temperatures (500–640 °C). Four calcination temperatures (400, 500, 600, and 700 °C) were investigated, with the results showing that the calcination temperature strongly affected catalytic properties, such as the crystalline phases, elemental distribution, physical properties, and catalytic basicity, leading to a wide range in catalytic performances. The catalyst calcined at 400 °C was superior among the catalysts, with 8.3 % C2+ yield, 24.8 % C2+ selectivity, and 33.6 % CH4 conversion at 640 °C. Furthermore, the catalyst was robust over 24 h of testing.

Photochemical nitrene transfer reactions of iminoiodinanes with sulfoxides

Nitrene, as an important and intriguing versatile synthon, is widely utilized for the formation of diverse nitrogenous skeletons under thermal or photochemical conditions. Typically, the N-sulfonyl nitrenes could be smoothly generated from iminoiodinanes at relatively low reaction temperatures to generate N-sulfonyl nitrenes. Herein, we described the direct immidation reaction of iminoiodinanes with sulfoxides through a blue-light-induced nitrenes transfer process. This strategy offers an efficient and gentle pathway for directly obtaining sulfoximines within a reaction time of only 10 ​min. Moreover, the reaction conditions do not necessitate the exclusion of moisture or air, rendering this photocatalytic amination reaction highly practical. A broad range of iminoiodinanes were well tolerated and reacted with sulfoxides smoothly to give the corresponding products in moderate to good yields, which provides a practical and green protocol to access N-sulfonyl architectures.

Influence of metal ions (Me: Fe, Cu, Co, Ni, Mn, Cr) on direct Z-scheme photocatalysts CN/Me-BTC on the degradation efficiency of tetracycline in water environment

BackgroundThe World Health Organization (WHO) reports that antibiotic resistance contributes to approximately 700,000 deaths yearly, with estimate suggesting a rise to 10 million deaths over the next 35 years. MethodsIn this study, direct Z-scheme heterojunction photocatalysts CN/Me-BTC (CN: graphite carbon nitride, Me: metal ions, BTC: benzene-1,3,5-tricarboxylic acid) were successfully synthesized using a hydrothermal combined microwave method, eliminating the need for toxic solvents and featuring a short crystallization time and low reaction temperature. Significant findingsThe study also explores the influence of various metal ions (Fe, Ni, Co, Mn, Cr, and Cu) on the morphological, physicochemical properties, and photocatalytic efficiency of tetracycline (TC) degradation. The CN/Me-BTC photocatalysts exhibit remarkable characteristics, including high visible light absorption, high surface area, low recombination rate between electrons and holes, and fast charge transfer ability.Among the synthesized photocatalysts, CN/FeBTC stands out with the highest efficiency in TC degradation (97.18 %) and degradation rate (decay constant k = 0.0197 min−1), surpassing CN by four times. The study comprehensively investigates factors influencing the TC degradation process, including catalyst mass, pH, antibiotic concentration, participating radicals, anions, and water sources. The mechanism of the photocatalytic process is elucidated based on radical quenching experiments and electrochemical properties.

Study on H3PO4-activated carbon catalytic co-pyrolysis of bamboo and LDPE to poly-generation syngas and aromatics at low temperature

Biomass-derived carbon activated by H3PO4 was adopted to catalytic co-pyrolysis of bamboo and low-density polyethylene (LDPE) to produce syngas and aromatics on a fixed bed reactor. Effects of LDPE ratio in the feedstock, catalytic co-pyrolysis temperature and ratio of catalyst to feedstock on the yields and compositions of the products were investigated. The increase of LDPE ratio in liquid first improved and then reduced the relative content of aromatics, while it showed a positive effect on the yield and the H2/CO ratio of gas. 500℃ was an optimum temperature, under which the relative content of aromatics in liquid kept higher, meanwhile, avoided the undesirable polymerization reactions of monocyclic aromatics. At the same time, the content of H2 in gas reached a maximum (59.3%), which was in favor of poly-generation. H3PO4-activated carbon catalyst (H3PO4-ACC) with abundant functional groups on surface catalyzed cracking, hydrodeoxygenation, cyclization and aromatization reactions so as to facilitate the generation of aromatics. Non-condensable gas was dry reformed on P-ACC at the expense of CO2, CH4 and CO to generate char and H2. When the reaction condition was at a LDPE ratio of 50%, a catalyst/feedstock ratio of 2:1 and at 500℃, the relative content of aromatics in liqiud was 81.65% and the proportion of syngas component in gas was 79.73%. The volume ratio of H2/CO approached to 3:1 in gas under this condition. H3PO4-ACC catalytic co-pyrolysis of bamboo and LDPE could obtain high quality gas and liquid products at a relative low reaction temperature, which provided a new research idea on high-value application of biomass and waste plastics.

Comparative Evaluation on Enhancing Fuel Properties of Biocoal from Bagasse Using Hydrothermal Carbonization and Torrefaction Processes

This research investigates the thermochemical conversion of sugarcane bagasse into biocoal using a subcritical aqueous medium (water, 200–250°C) and a limited oxygen atmosphere (nitrogen, 250–300°C). The aim is to discover alternative renewable energy sources to replace fossil fuels. The effects of those different methods on the physiochemical properties of the solid product were determined. The best results of fixed carbon (37.13%), carbon content (62.17%), fuel ratio (0.61), and higher heating value (HHV) (25.75 MJ/kg) were obtained under hydrothermal carbonization (HTC) at 250°C. Additionally, the HTC process effectively reduced the ash and sulphur content of the solid products. Moreover, HTC was found to be a promising method for depolymerizing hemicellulose. Hydrochar produced at 250°C is located within the range of lignite, which is typically obtained at lower reaction temperatures compared to biochar samples. Consequently, the conversion of sugarcane bagasse into solid biofuel through HTC shows great potential from a thermochemical perspective.

APPLICATION OF ATOMIC OXYGEN FOR GASOLINE OCTANE NUMBER DETERMINATION

There is a method that measures the thermal effect of a low-temperature oxidation reaction to determine the octane number of gasoline. The reaction was conducted in the presence of ozone on a thermistor surface at a temperature of the vapor-gas mixture equal to the end boiling point of gasoline in order to lower the analysis temperature. Keywords: low-temperature oxidation, atomic oxygen, gasoline, detonation resistance, octane number, ozone, and thermistor.

Low temperature catalytic activity of molybdenum promoted two-dimensional boron nitride in propane oxidative dehydrogenation reaction

The catalytic oxidation dehydrogenation of propane to propylene, achieved at low temperatures and with high selectivity on catalysts supported by non-noble metals, exhibits significant potential for a wide range of applications. The performance of boron-based catalysts in ODHP is remarkable; however, there is a dearth of research on their low-temperature range performance. The present study employed a straightforward impregnation method to synthesize a range of Mo/h-BN-γ-Al2O3 catalysts with varying molybdenum loadings, focusing on the comparison between commercial h-BN and h-BN-γ-Al2O3 mixed support. The Mo/h-BN-γ-Al2O3 catalyst demonstrates remarkable low-temperature ODHP activity, with an initial conversion rate of 2.36 % and a propylene selectivity of 96 % at a reaction temperature of 260 ℃, exhibiting good stability over 50 h, the catalytic performance of Mo/h-BN-γ-Al2O3 in the low-temperature range surpasses that of commercial h-BN by a significant margin. Comparative experiments, along with physical and chemical characterization techniques, demonstrate that the incorporation of an appropriate quantity of Mo enhances the catalyst's acidity and redox capability. Furthermore, the synergistic effect between MoOx and BOx promotes low-temperature ODHP. The mechanism underlying the catalyst's low-temperature reaction was investigated using in-situ infrared spectroscopy technology.

Microwave-assisted catalytic technology for sustainable production of valuable chemicals from plastic waste with enhanced catalyst reusability

High energy consumption and catalyst deactivation hinder thermal plastic waste decomposition for chemical production. This study employs a microwave-assisted catalytic process with Ru/ZSM-5 as the catalyst for polyethylene waste. At 300 °C under the first cycle of microwave heating, gas yield reaches 90 wt%, with 23 wt% aromatics selectivity and 30 wt% light olefins selectivity. In the first cycle of thermal heating, gas yield is 72 wt%, with 67 wt% alkanes and 32 wt% light olefins selectivity. In microwave cycle reactions, gas yield remains around 88 wt% through seven cycles over the spent catalyst (without regeneration), shifting product composition to 80 wt% light olefins in the 7th cycle. In contrast, in thermal cycle reactions, catalyst activity is lost after one cycle, and gas yield drops from 72 wt% to 45 wt%. Microwave-assisted catalytic technology shows potential for economically producing valuable chemicals from plastic waste, as lower reaction temperature and high catalyst reusability.

The Mechanism of Rh(I)-Catalyzed Coupling of Benzotriazoles and Allenes Revisited: Substrate Inhibition, Proton Shuttling, and the Role of Cationic vs Neutral Species.

Direct coupling of benzotriazole to unsaturated substrates such as allenes represents an atom-efficient method for the construction of biologically and pharmaceutically interesting functional structures. In this work, the mechanism of the N2-selective Rh complex-catalyzed coupling of benzotriazoles to allenes was investigated in depth using a combination of experimental and theoretical techniques. Substrate coordination, inhibition, and catalyst deactivation was probed in reactions of the neutral and cationic catalyst precursors [Rh(μ-Cl)(DPEPhos)]2 and [Rh(DPEPhos)(MeOH)2]+ with benzotriazole and allene, giving coordination, or coupling of the substrates. Formation of a rhodacycle, formed by unprecedented 1,2-coupling of allenes, is responsible for catalyst deactivation. Experimental and computational data suggest that cationic species, formed either by abstraction of the chloride ligand or used directly, are relevant for catalysis. Isomerization of benzotriazole and cleavage of its N-H bond are suggested to occur by counteranion-assisted proton shuttling. This contrasts with a previously proposed scenario in which oxidative N-H addition at Rh is one of the key steps. Based on the mechanistic analysis, the catalytic coupling reaction could be optimized, leading to lower reaction temperature and shorter reaction times compared to the literature.

Preparation and microstructure of Cu-Al2O3 composites by a novel supercritical water liquid phase in-situ reaction method

The high solubility, reactivity and solubility of supercritical water provide a new way for the preparation of advanced metal matrix composites. In this paper, Cu-Al2O3 composites are prepared by supercritical water liquid phase in situ reaction (SW-LIR). In this method, the Cu-Al atomized alloy powder are used as raw material, deionized water as reaction medium, H2O2 as liquid phase oxygen source, and the Cu-Al2O3 composite powder are prepared at 380 ℃ and 22.1 MPa for 10 min. The Cu-Al2O3 composite block is prepared by spark plasma sintering (SPS). The results show that Al2O3 has an average size of 41.8 nm and mainly exists in the form of mixed crystals. The interface with the matrix is coherent or semi-coherent. With the increase of Al2O3 content, the mechanical properties of the composites are obviously improved. When the Al2O3 content is 1.12 wt%, the microhardness is as high as 164.52 HV and the tensile strength is 441 MPA, while still maintaining a high electrical conductivity (75 %IACS). At the same time, it shows quite excellent high temperature performance. It can still retain the characteristics of high strength at 1000℃, which solves the shortcomings of high thermal conductivity but low strength of pure copper. Compared with the traditional method, SW-LIR method has the characteristics of low reaction temperature, fast reaction speed and green environmental protection.

Revealing the mechanisms of NH3 adsorption and reactions in catalytic NOx reduction over Cux/CHA zeolites by in situ DRIFTS spectroscopy

Adsorption and activation of NH3 on Cu-SSZ-13 were essential for NOx removal, however, their important role at the molecular level remains unclear. In this work, the Al-rich Cu/SSZ-13 (Cux/CHA) catalysts were synthesized by the incipient-wetness impregnation method, and the NH3-SCR performance was investigated. It is found that high Cu content promoted the formation of Z-[Cu(OH)]+ and CuOx particles, enhanced the adsorption capacity of NOx, and increased the intra-zeolite oxolation process in the Cux/CHA catalysts. In situ DRIFTS results showed that the Z-[Cu(OH)(NH3)x]+(x<3) exhibited analogous properties to B-NH4+, but it would convert to Z-[Cu(OH)(NH3)3]+ with increasing NH3 adsorption time and exhibit L-NH3 properties. Those findings could provide a new insight into understanding the adsorption and activation of NH3 in low-temperature reactions, as well as new ideas for improving NOx conversion during cold start.