Effect of the graphitic degree of carbon supports on the catalytic performance of ammonia synthesis over Ba-Ru-K/HSGC catalyst

A series of high surface area graphitic carbon materials （HSGCs） were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x （x is the ball-milling time in hour） catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl_3/SiO_2-templated approach

Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance.Hence,searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology.Here,we report a Ba‐K/Ru‐MC catalyst with Ru particle size of 1.5–2.5 nm semi‐embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba‐Ru‐K/MC catalyst,although both have similar metal particle sizes for ammonia synthesis.Further,the Ba‐K/Ru‐MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts.Characterization techniques such as high‐resolution transmission electron microscopy,N2 physisorption,CO chemisorption,and temperature‐programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba‐K/Ru‐MC,which may facilitate electron transport better than supported nanoparticles.

Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination

The development of efficient and stable non-mercury catalysts for the chlor-alkali industry is desirable but remains a great challenge.Herein,we design a series of ruthenium catalysts for acetylene hydrochlorination by regulating the electronic structure of ruthenium ions through coordination with various ligands(thiourea,phenanthroline,and L-lactic).The turnover frequencies(TOFs)and apparent activation energies for the acetylene hydrochlorination have a linear relationship with the binding energy of Ru3+in the ruthenium catalysts.The synergetic effect of the ruthenium ion and ligands plays an important role in acetylene hydrochlorination.The Ru-Thi/AC catalyst with thiourea as the ligand shows the highest TOF and stability in acetylene hydrochlorination.The present study provides a rational method to regulate the electronic structure of supported metal catalysts with high catalytic performance exhibited by the carbon-supported heterogeneous catalysts.

The origin of the extraordinary stability of mercury catalysts on the carbon support: the synergy effects between oxygen groups and defects revealed from a combined experimental and DFT study

Thermal stability of HgCl2 has a pivotal importance for the hydrochlorination reaction as the loss of mercuric compounds is toxic and detrimental to environment.Here we report a low-mercury catalyst which has durability over 10000 h for acetylene hydrochlorination under the industrial condition.The stability of the catalyst is carefully analyzed from a combined experimental and density functional theory study.The analysis shows that the extraordinary stability of mercury catalyst is resulted from the synergy effects between surface oxygen groups and defective edge sites.The binding energy of HgCl2 is increased to be higher than 130 kJ/mol when adsorption is at the edge site with a nearby oxygen group.Therefore,the present study revealed that the thermal stability problem of mercury-based catalyst can be solved by simply adjusting the surface chemistry of activated carbon.Furthermore,the reported catalyst has already been successfully applied in the commercialized production of vinyl chloride.

Human-induced landslide on a high cut slope: a case of repeated failures due to multi-excavation

The paper attempts to represent a case of repeated failures on a high cut slope due to multi-excavation. The characteristics of each failure induced by excavation are analyzed through geological investigation, and then a geological model at different failure stages is proposed. The geological analysis shows that the excavation-induced repeated failures are related to the exposure of the weak bedding plane and the toe unloading of the cut slope, Numerical modeling is conducted based on a sequential method, taking into account the main failure stages of cut slope. The simulation results fairly coincide with the practical phenomena observed in field. It is shown that the decrease in normal stress of displaced mass on cut slope will induce the increase in shear stress in bedding planes and that at the toe of the cut slope. The released stress leads to repeated gravitational instabilities of cut slope due to the decrease in normal stress and the increase in shear stress along the bedding planes of mudstone.

Role of surface defects of carbon nanotubes on catalytic performance of barium promoted ruthenium catalyst for ammonia synthesis

Carbon nanotubes(CNTs) with abundant surface defects are prepared by a liquid oxidation and thermal annealing method. The defective CNTs-D supported Ba–Ru/CNTs-D catalysts exhibit superior catalytic performance in ammonia synthesis with a TOF be increased up to 0.30 s-1, which is 2.5 times of oxidized CNTs-O supported Ba–Ru/CNTs-O catalysts and 5 times of the Ba–Ru/CNTs. The characterizations by CO chemisorption, transmission electron microscope, Raman, and X-ray photoelectron spectroscopy revealed that the uniformly well dispersed Ru NPs can be stabilized on the defective sites of CNTs-D. The great improvement of the catalytic performance and stability of the Ba–Ru/CNTs-D is contributed to the strong interaction between Ru NPs and surface defect of the CNTs.

A non-opioid pathway for dynorphin-caused spinal cord injury in rats

Intrathecal injection of dynorphin into rats via subarachnoid catheter induces damage to spinal cord tissue and motor function. Injection of the kappa opioid receptor antagonist nor-binaltorphine, or the excitatory amino acid N-methyl-D-aspartate receptor antagonist MK-801 into rats alleviated the pathological changes of dynorphin-caused spinal cord tissue injury and reduced the acid phosphatase activity in the spinal cord. The experimental findings indicate that there are opioid and non-opioid pathways for dynorphin-induced spinal cord injury, and that the non-opioid receptor pathway may be mediated by the excitatory amino acid N-methyl-D-aspartate receptor.

Kappa opioid receptor antagonist and N-methyl-D-aspartate receptor antagonist affect dynorphin-induced spinal cord electrophysiologic impairment

The latencies of motor- and somatosensory-evoked potentials were prolonged to different degrees, and wave amplitude was obviously decreased, after injection of dynorphin into the rat subarachnoid cavity. The wave amplitude and latencies of motor- and somatosensory-evoked potentials were significantly recovered at 7 and 14 days after combined injection of dynorphin and either the kappa opioid receptor antagonist nor-binaltorphimine or the N-methyl-D-aspartate receptor antagonist MK-801. The wave amplitude and latency were similar in rats after combined injection of dynorphin and nor-binaltorphimine or MK-801. These results suggest that intrathecal injection of dynorphin causes damage to spinal cord function. Prevention of N-methyl-D-aspartate receptor or kappa receptor activation lessened the injury to spinal cord function induced by dynorphin.

La_2Ce_2O_7 supported ruthenium as a robust catalyst for ammonia synthesis

La_2Ce_2O_7 nanoparticles were prepared by citric acid complexation method followed by calcination at varied temperatures. Then, supported with 4 wt% Ru, they were evaluated as the catalysts for ammonia synthesis under conditions similar with industry. With La_2Ce_2O_7 being calcinated at 700 or 800℃, the experimental results indicate that the Ru/La_2Ce_2O_7 catalyst exhibits much higher ammonia concentration or ammonia synthesis rate than that of Ru/CeO_2 and Ru/La_2O_3. In addition, Ru/La_2Ce_2O_7 possesses high stability under over-heating test. In the absence of any promotor, ammonia concentration of Ru/La_2Ce_2O_7 catalyst approaches 14% at 450℃, GHSV of 10000 h^(-1) and pressure of 10 MPa. The rate-determining step of ammonia synthesis, dissociation of N_2 is significantly facilitated by the strong metalesupport interaction(SMSI) between Ru and La_2Ce_2O_7. Due to the interaction, La_2Ce_2O_7 tends to donate electrons to Ru,resulting in the high electron density over the surface of Ru active sites which is favorable for the dissociation of N_2. Consequently, high activity is achieved.