Non-classical Deactivation Mechanism in a Supported Intermetallic Catalyst for Propane Dehydrogenation.

Platinum-based supported intermetallic alloys (IMAs) demonstrate exceptional performance in catalytic propane dehydrogenation (PDH) primarily because of their remarkable resistance to coke formation. However, these IMAs still encounter a significant hurdle in the form of catalyst deactivation. Understanding the complex deactivation mechanism of supported IMAs, which goes beyond conventional coke deposition, requires meticulous microscopic structural elucidation. In this study, we unravel a nonclassical deactivation mechanism over a PtZn/γ-Al2O3 PDH catalyst, dictated by the PtZn to Pt3Zn nanophase transformation accompanied with dezincification. The physical origin lies in the metal support interaction (MSI) that enables strong chemical bonding between hydroxyl groups on the support and Zn sites on the PtZn phase to selectively remove Zn species followed by the reconstruction towards Pt3Zn phase. Building on these insights, we have devised a solution to circumvent the deactivation by passivating the MSI through surface modification of γ-Al2O3 support. By exchanging protons of hydroxyl groups with potassium ions (K) on the γ-Al2O3 support, such a strategy significantly minimizes the dezincification of PtZn IMA via diminished metal-support bonding, which dramatically reduces the deactivation rate from 0.2044 to 0.0587 h-1.

Research on orchard navigation method based on fusion of 3D SLAM and point cloud positioning.

Accurate navigation is crucial in the construction of intelligent orchards, and the need for vehicle navigation accuracy becomes even more important as production is refined. However, traditional navigation methods based on global navigation satellite system (GNSS) and 2D light detection and ranging (LiDAR) can be unreliable in complex scenarios with little sensory information due to tree canopy occlusion. To solve these issues, this paper proposes a 3D LiDAR-based navigation method for trellis orchards. With the use of 3D LiDAR with a 3D simultaneous localization and mapping (SLAM) algorithm, orchard point cloud information is collected and filtered using the Point Cloud Library (PCL) to extract trellis point clouds as matching targets. In terms of positioning, the real-time position is determined through a reliable method of fusing multiple sensors for positioning, which involves transforming the real-time kinematics (RTK) information into the initial position and doing a normal distribution transformation between the current frame point cloud and the scaffold reference point cloud to match the point cloud position. For path planning, the required vector map is manually planned in the orchard point cloud to specify the path of the roadway, and finally, navigation is achieved through pure path tracking. Field tests have shown that the accuracy of the normal distributions transform (NDT) SLAM method can reach 5 cm in each rank with a coefficient of variation that is less than 2%. Additionally, the navigation system has a high positioning heading accuracy with a deviation within 1° and a standard deviation of less than 0.6° when moving along the path point cloud at a speed of 1.0 m/s in a Y-trellis pear orchard. The lateral positioning deviation was also controlled within 5 cm with a standard deviation of less than 2 cm. This navigation system has a high level of accuracy and can be customized to specific tasks, making it widely applicable in trellis orchards with autonomous navigation pesticide sprayers.

Engineering nanoscale H supply chain to accelerate methanol synthesis on ZnZrOx.

Metal promotion is the most widely adopted strategy for enhancing the hydrogenation functionality of an oxide catalyst. Typically, metal nanoparticles or dopants are located directly on the catalyst surface to create interfacial synergy with active sites on the oxide, but the enhancement effect may be compromised by insufficient hydrogen delivery to these sites. Here, we introduce a strategy to promote a ZnZrOx methanol synthesis catalyst by incorporating hydrogen activation and delivery functions through optimized integration of ZnZrOx and Pd supported on carbon nanotube (Pd/CNT). The CNT in the Pd/CNT + ZnZrOx system delivers hydrogen activated on Pd to a broad area on the ZnZrOx surface, with an enhancement factor of 10 compared to the conventional Pd-promoted ZnZrOx catalyst, which only transfers hydrogen to Pd-adjacent sites. In CO2 hydrogenation to methanol, Pd/CNT + ZnZrOx exhibits drastically boosted activity-the highest among reported ZnZrOx-based catalysts-and excellent stability over 600 h on stream test, showing potential for practical implementation.

Stable catalysis of neutral silica-supported potassium lactate for vapour-phase dehydration of lactic acid to acrylic acid - critical role of the support.

We have deeply investigated KNO3-derived silica-supported potassium lactate catalysts for the vapour-phase dehydration of lactic acid (LA) to acrylic acid (AA) by catalytic testing, IR spectroscopic monitoring, ammonia temperature-programmed desorption, isopropyl amine temperature-programmed desorption, IR spectroscopy of pyridine adsorption and thermogravimetric analysis (TGA). A combination of catalytic and acid property studies illustrates that the acidic KNO3/silica systems are not favourable for catalytic selectivity and stability for the production of AA whereas the neutral KNO3/silica systems favour catalytic selectivity and stability for the production of AA. A combination of catalytic and TGA studies indicates that the interaction between KNO3 and silica has a strong promotional effect on catalytic stability for the production of AA. A combination of IR monitoring and catalytic studies suggests that the effects of the surface acidity and the interactions between the potassium salt or base and silica on the catalytic performance are associated with the content and stability of potassium lactate as the catalytic active species. The catalyst stabilization and deactivation under LA dehydration conditions are discussed in detail. The neutral KNO3/silica systems enable the formation of potassium lactate to become dominant whereas the unsupported KNO3 and acidic KNO3/silica systems lead to the formation of poly(potassium acrylate), i.e. catalyst deactivation. This contribution includes for the first time that the dehydration of LA to AA proceeds smoothly with a neutral heterogeneous catalyst.

Research on damage mechanism and protection of the collision penetration of the thin-walled long rod structure.

Traffic accidents have been closely concerned by the society, and the serious traffic accidents caused by vehicle and guardrail collisions are one of the main manifestations. However, the research in the field of vehicle and guardrail collisions is mainly limited to the waveform guardrail on the expressway, and there is little research on the urban road guardrail, especially in the secondary damage caused by guardrails field. Moreover, the collision between vehicle and the rectangular guardrail of city road is easy to form thin-walled long rod, and it penetrates the driver's chest. To evaluate and analyze the injury results and mechanism of this phenomenon, a penetrating finite element model of chest bone characterized by Chinese human is established using the medical software (MIMICS) and engineering software (HYPERMESH). The model validation is mainly dependent on the corpse impact test. In addition, the software (LS-DYNA) is deployed to simulate the thin-walled long rod penetration. According to the analysis of the "PENETRATION," it is found that the cavity effect produced by the thin-walled long rod through the chest, and the degree of chest damage is related to the speed, angle, weight, and stability of the thin-walled long rod. The difference between the peak value of collision corpse experiment and simulation peak value is less than 5%, which implies that the model is reasonable. Besides, the simulation results also confirm the accident and medical diagnosis cases. As a common form of secondary injury in traffic accidents and a typical case of medical penetrating injury, the thin-walled long rod penetrating injury has important reference value for studies in both directions.

In Situ-Generated Supported Potassium Lactate: Stable Catalysis for Vapor-Phase Dehydration of Lactic Acid to Acrylic Acid.

We have studied unsupported, silica gel- and amorphous silica-alumina-supported catalysts derived from K salts for the vapor-phase dehydration of lactic acid (LA) to acrylic acid (AA). A catalytic study shows that the supported catalysts improve the activity and selectivity for the production of AA and decrease the selectivity for the production of propionic acid (PA). The silica-alumina-supported catalysts remain fairly stable in the catalytic performance during 90 h of reaction. The IR spectroscopic characterization combined with the catalytic study demonstrates that potassium lactate (C3H5KO3) in situ generated from LA and a K salt is an important reaction intermediate for the production of AA and the catalytic stability is associated with the chemical stability of C3H5KO3 and the activity for the regeneration of C3H5KO3 in the catalytic cycle. On silica-alumina, C3H5KO3 is well stabilized and smoothly regenerated during the reaction, leading to the good catalytic stability. This work suggests for the first time that lactate salt acts as the true catalytic active species for the dehydration of LA to AA. We also propose a predominant reaction pathway for the vapor-phase dehydration of LA to AA with K salt catalyst systems.

Transformation of Stöber Silica Spheres to Hollow Hierarchical Single-Crystal ZSM-5 Zeolites with Encapsulated Metal Nanocatalysts for Selective Catalysis.

The activity of zeolite-supported nanocatalysts is dependent on both the dispersion, size, and location of metal nanoparticles around the zeolite and the size and pore structure of the zeolite. In this study, a synthetic approach was developed to encapsulate metal catalysts within hollow interiors of single-crystal ZSM-5. Briefly, Stöber silica spheres were synthesized and then transformed to single-crystal nano-ZSM-5 (Si/Al = 60), followed by growth of embedded metal nanoparticles and subsequently creation of a nanosized (30-50 nm shell thickness) hollow hierarchical zeolite structure. Metal nanoparticles such as Co, Cu, Cu-Zn, Fe, and Ni can be supported on the inner wall of the hollow zeolite and the surrounding satellite mesopores, without any particles present on the external zeolite surface. When evaluated as a catalyst for the Fischer-Trøpsch reaction, the Fe@h-ZSM5 catalyst shows high activity, sintering and coking resistance (50% longer stability than Fe@ZSM5), and secondary cracking reactions in the acid sites in the ZSM-5 shell, which reduce C5+ hydrocarbon selectivity and increase smaller-chain hydrocarbon selectivity. In addition, when Pt was further deposited inside the hollow structure, shape-selective alkene hydrogenation was demonstrated. These configured nanoscale zeolite catalysts have potential applications for reactions that involve supported metal nanoparticle catalysis, shape selectivity, or secondary cracking reactions.

The role of metal-support interaction for CO-free hydrogen from low temperature ethanol steam reforming on Rh-Fe catalysts.

Rh-Fe catalysts supported on Ca-Al2O3, MgO and ZrO2 were evaluated in ethanol steam reforming at 623 K and compared to Rh catalysts on the same supports without iron promotion. The metal-support interaction among the three entities, i.e. Rh ↔ Fe2O3 ← support (ZrO2, MgO and Ca-Al2O3) was investigated using H2-chemisorption, TEM, XPS and in situ techniques such as DRIFTS, temperature-resolved XRD and XAS. As compared to the unpromoted Rh catalysts on the same supports, the CO selectivity is depressed in the presence of iron on Rh/MgO and Rh/Ca-Al2O3, the latter being significantly superior. The role of metal-support interaction for CO-free hydrogen generation was unravelled using a combination of techniques. It was found that the reducibility of iron oxide determines the extent of the strong metal support interaction between Rh and Fe2O3 and the reducibility of iron oxide was affected by the support. On Rh-Fe/Ca-Al2O3, a good balance of the interaction between Rh, Fe2O3 and Ca-Al2O3 prevents strong metal support interaction between Rh and Fe2O3 and thus promotes CO elimination via water-gas-shift reaction on Rh-FexOy sites.

Preparation of supercapacitor electrodes through selection of graphene surface functionalities.

In order to investigate the effect of graphene surface chemistry on the electrochemical performance of graphene/polyaniline composites as supercapacitor electrodes, graphene oxide (G-O), chemically reduced G-O (RG-O), nitrogen-doped RG-O (N-RG-O), and amine-modified RG-O (NH(2)-RG-O) were selected as carriers and loaded with about 9 wt % of polyaniline (PANi). The surface chemistry of these materials was analyzed by FTIR, NEXAFS, and XPS, and the type of surface chemistry was found to be important for growth of PANi that influences the magnitude of increase of specific capacitance. The NH(2)-RG-O/PANi composite exhibited the largest increase in capacitance with a value as high as 500 F g(-1) and good cyclability with no loss of capacitance over 680 cycles, much better than that of RG-O/PANi, N-RG-O/PANi, and G-O/PANi when measured in a three-electrode system. A NH(2)-RG-O/PANi//N-RG-O supercapacitor cell has a capacitance of 79 F g(-1), and the corresponding specific capacitance for NH(2)-RG-O/PANi is 395 F g(-1). This research highlights the importance of introducing -NH(2) to RG-O to achieve highly stable cycling performance and high capacitance values.

The effect of trivalent cations on the performance of Mg-M-CO(3) layered double hydroxides for high-temperature CO(2) capture.

The effect of trivalent cations on the performance of Mg-M-CO(3) (M=Al, Fe, Ga, Mn) layered double hydroxides (LDHs) for high-temperature CO(2) capture is systematically investigated for the first time. We demonstrate that the M(3+) determines the structure evolution of LDH derivatives under thermal treatment, and finally influences the CO(2) capture capacity. Very different calcination temperatures are required for the different LDHs to obtain their maximum CO(2) capture capacities. To have a clear understanding of the reason behind these big differences the physicochemical properties, thermal stability, and memory effect of the LDHs were investigated. Both the thermal stability and the memory effect of LDHs are greatly influenced by the type of trivalent cation. The CO(2) capture capacities were also evaluated under various conditions. Another important finding of this work is that the quasi-amorphous phase obtained by thermal treatment at the lowest possible temperature gives the highest CO(2) capture capacity.

The role of acidic sites and the catalytic reaction pathways on the Rh/ZrO2 catalysts for ethanol steam reforming.

Rh catalysts supported on ZrO(2)-based oxides were studied for ethanol steam reforming (SR) reaction. Pure ZrO(2) as the support resulted in higher H(2) production yield compared to the ZrO(2) oxide decorated with CeO(2), Al(2)O(3), La(2)O(3) or Li(2)O at the reaction temperature of 300 degrees C. Above 450 degrees C, all the catalysts exhibited similar catalytic activity. However, at low reaction temperatures (below 400 degrees C), a significant enhancement in the catalytic activity, selectivity and stability was achieved by replacing the ZrO(2) support prepared by a precipitation method (ZrO(2)-CP) with that prepared by a hydrothermal method (ZrO(2)-HT). A deactivation was observed during the EtOH SR reaction at 300 degrees C on the two catalysts of Rh/ZrO(2)-CP and Rh/ZrO(2)-HT. NH(3)-TPD experiments confirmed that the ZrO(2)-HT support had two types of acidic sites while the ZrO(2)-CP support had only one type of weak acidic sites. DRIFTS studies showed that the absorption of EtOH molecules was strong on the Rh/ZrO(2)-HT catalyst and a number of C(2) oxygenates were accumulated on the catalyst surface. Meanwhile, the EtOH absorption on the Rh/ZrO(2)-CP catalyst was weak and the accumulation of CO, carbonate and CH(x) was observed. It is concluded that the relatively strong Lewis acidic sites in the Rh/ZrO(2)-HT catalyst is responsible for the strong absorption of EtOH molecules, and the subsequent C-H breakage step (formation of acetaldehyde or called as dehydrogenation reaction) is a fast reaction on it; on the Rh/ZrO(2)-CP catalyst, the EtOH adsorption was weak and the C-C breakage was the dominating reaction which led to the accumulation of surface CO, CH(x) and CO(2) species. Therefore, it is believed that, in order to promote the absorption of EtOH molecules and to reduce the formation of metastable carbonaceous species (C(2) oxygenates) during the reaction, the catalyst should be enhanced both with Lewis acidity and with C-C bond breakage function. Also, it was found that the Rh particle size and distribution, as well as the surface area of the catalyst, were not important factors in determining the catalytic performance.

Controlled synthesis, characterization, and catalytic properties of Mn(2)O(3) and Mn(3)O(4) nanoparticles supported on mesoporous silica SBA-15.

A method established in the present study has proven to be effective in the synthesis of Mn(2)O(3) nanocrystals by the thermolysis of manganese(III) acetyl acetonate ([CH(3)COCH=C(O)CH(3)](3)-Mn) and Mn(3)O(4) nanocrystals by the thermolysis of manganese(II) acetyl acetonate ([CH(3)COCH=C(O)-CH(3)](2)Mn) on a mesoporous silica, SBA-15. In particular, Mn(2)O(3) nanocrystals are the first to be reported to be synthesized on SBA-15. The structure, texture, and electronic properties of nanocomposites were studied using various characterization techniques such as N2 physisorption, X-ray diffraction (XRD), laser Raman spectroscopy (LRS), temperature-programmed reduction (TPR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The results of powder XRD at low angles show that the framework of SBA-15 remains unaffected after generation of the manganese oxide (MnO(x)) nanoparticles, whereas the pore volume and the surface area of SBA-15 dramatically decreased as indicated by N2 adsorption-desorption. TEM images reveal that the pores of SBA-15 are progressively blocked with MnO(x) nanoparticles. The formation of the hausmannite Mn(3)O(4) and bixbyite Mn(2)O(3) structures was clearly confirmed by XRD. The surface structures of MnO(x) were also determined by LRS, XPS, and TPR. The crystalline phases of MnO(x) were identified by LRS with corresponding out-of-plane bending and symmetric stretching vibrations of bridging oxygen species (M-O-M) of both MnO(x) nanoparticles and bulk MnO(x). We also observed the terminal Mn=O bonds corresponding to vibrations at 940 and 974 cm-1 for Mn(3)O(4)/SBA-15 and Mn(2)O(3)/SBA-15, respectively. These results show that the MnO(x) species to be highly dispersed inside the channels of SBA-15. The nanostructure of the particles was further identified by the TPR profiles. Furthermore, the chemical states of the surface manganese (Mn) determined by XPS agreed well with the findings of LRS and XRD. These results suggest that the method developed in the present study resulted in the production of MnO(x) nanoparticles on mesoporous silica SBA-15 by controlling the crystalline phases precisely. The thus-prepared nanocomposites of MnO(x) showed significant catalytic activity toward CO oxidation below 523 K. In particular, the MnO(x) prepared from manganese acetyl acetonate showed a higher catalytic reactivity than that prepared from Mn(NO(3))2.

Ultrasound-assisted polyol method for the preparation of SBA-15-supported ruthenium nanoparticles and the study of their catalytic activity on the partial oxidation of methane.

Metallic Ru nanoparticles have been successfully produced and incorporated into the pores of SBA-15 in situ employing a simple ultrasound-assisted polyol method. The product has been confirmed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy, where ultrasound provides both the energy for the reduction of the Ru(III) ion and the driving force for the loading of the Ru(0) nanoparticles into the SBA-15 pores. An ultrasound-assisted insertion mechanism has been proposed based on the microjets and shake-wave effect of the collapsed bubbles. The catalytic properties of the SBA-15-supported Ru nanoparticles have been tested by the partial oxidization of methane and show very high activity and high CO selectivity.