Cu is the only monometallic catalyst that produces a large amount of hydrocarbon fuels during the CO2 electrochemical reduction reaction (CO2RR). However, the CO2RR mechanism and the impact of ...electrolyte are unclear. In this communication, two important issues regarding the CO2RR on Cu surfaces are studied: (1) the direct observation on reaction intermediates and (2) the role of the electrolyte (KHCO3) in the reaction. Surface-enhanced infrared absorption spectroscopy allows direct observation of several reaction intermediates that have never been detected before, except for the commonly detected CO. Another important finding is that CO2 molecules are mediated to the Cu surface via their equilibrium with bicarbonate anions instead of direct adsorption from the solution. These results shed light on the full understanding of the CO2RR on Cu surfaces and developing more advanced catalysts.
Facile interconversion between CO2 and formate/formic acid (FA) is of broad interest in energy storage and conversion and neutral carbon emission. Historically, electrochemical CO2 reduction reaction ...to formate on Pd surfaces was limited to a narrow potential range positive of −0.25 V (vs RHE). Herein, a boron-doped Pd catalyst (Pd–B/C), with a high CO tolerance to facilitate dehydrogenation of FA/formate to CO2, is initially explored for electrochemical CO2 reduction over the potential range of −0.2 V to −1.0 V (vs RHE), with reference to Pd/C. The experimental results demonstrate that the faradaic efficiency for formate (ηHCOO– ) reaches ca. 70% over 2 h of electrolysis in CO2-saturated 0.1 M KHCO3 at −0.5 V (vs RHE) on Pd–B/C, that is ca. 12 times as high as that on homemade or commercial Pd/C, leading to a formate concentration of ca. 234 mM mg–1 Pd, or ca. 18 times as high as that on Pd/C, without optimization of the catalyst layer and the electrolyte. Furthermore, the competitive selectivity ηHCOO–/ηCO on Pd–B/C is always significantly higher than that on Pd/C despite a decreases of ηHCOO– and an increases of the CO faradaic efficiency (ηCO) at potentials negative of −0.5 V. The density functional theory (DFT) calculations on energetic aspects of CO2 reduction reaction on modeled Pd(111) surfaces with and without H-adsorbate reveal that the B-doping in the Pd subsurface favors the formation of the adsorbed HCOO*, an intermediate for the FA pathway, more than that of *COOH, an intermediate for the CO pathway. The present study confers Pd–B/C a unique dual functional catalyst for the HCOOH ↔ CO2 interconversion.
The excavation of deep mining roadways with traditional mining methods leads to various issues, such as the occurrence of large deformations, the waste of coal resources, complex conditions and the ...high cost of advanced support measures. In this study, we examined the roadway damage mechanism of the traditional gob-side entry driving method with coal pillars using the Suncun Coal Mine, the deepest mine in China, as an engineering case study. A method for the automatic formation of roadways in deep mining areas by roof cutting with high-strength bolt-grouting was proposed, and several quantitative evaluation indicators, namely, the roadway deformation control rate, anchor cable strength utilization ratio, and hydraulic prop strength utilization ratio, were established. The impacts of controlling the deformation of the surrounding rock were comparatively analysed in consideration of numerous factors, such as the mechanical parameters of the surrounding rock, roof cutting height, roof cutting angle, grouting anchor cable length, and hydraulic prop spacing. On this basis, the proposed method was applied in the field. The results showed that the automatically formed roadway cross-section exhibited decreased convergence deformation; moreover, the roof deformation was effectively controlled, and the passive hydraulic prop supports could be effectively replaced with the active support of grouting anchor cables, verifying the effect of the proposed method.
To reduce the roadway drivage ratio, drivage cost, and safety accidents, and increase the resource recovery ratio, a no-pillar mining technique with automatically formed gob-side entry retaining is ...proposed for longwall mining. In this technique, pressure is offloaded via directional roof cutting, and a roadway is automatically formed via the ground pressure and rock breaking expansion. These processes permit the implementation of a new longwall mining process in which there is no mining roadway and no reserves of coal pillars. In this paper, the concepts and key techniques (the technique of directional roof cutting, the formation technique of integrated coal side of the automatically formed gob-side entry retaining, the formation technique of gob-side gangue rib, and the support technique using a constant-resistance and large-deformation anchor cable) of no-pillar mining with automatically formed gob-side entry retaining are introduced, and a field engineering test is performed. The test results are as follows: the no-pillar mining concepts and technique with automatically formed gob-side entry retaining are feasible; all techniques and processes fully satisfy field production requirements; and the deformation of the automatically formed gob-side entry retaining is small, and the control effect is significant. These results prove that the no-pillar mining technique with automatically formed gob-side entry retaining is feasible for longwall mining and achieves the goal of safe and efficient mining.
Automatically formed roadway (AFR) by roof cutting with bolt grouting (RCBG) is a new deep coal mining technology. By using this technology, the broken roadway roof is strengthened, and roof cutting ...is applied to cut off stress transfer between the roadway and gob to ensure the collapse of the overlying strata. The roadway is automatically formed owing to the broken expansion characteristics of the collapsed strata and mining pressure. Taking the Suncun Coal Mine as the engineering background, the control effect of this new technology on roadways was studied. To compare the law of stress evolution and the surrounding rock control mechanisms between AFR and traditional gob-side entry driving, a comparative study of geomechanical model tests on the above methods was carried out. The results showed that the new technology of AFR by RCBG effectively reduced the stress concentration of the roadway compared with gob-side entry driving. The side abutment pressure peak of the solid coal side was reduced by 24.3%, which showed an obvious pressure-releasing effect. Moreover, the position of the side abutment pressure peak was far from the solid coal side, making it more beneficial for roadway stability. The deformation of AFR surrounding rock was also smaller than the deformation of the gob-side entry driving by the overload test. The former was more beneficial for roadway stability than the latter under higher stress conditions. Field application tests showed that the new technology can effectively control roadway deformation. Moreover, the technology reduced roadway excavation and avoided resource waste caused by reserved coal pillars.
WRKY transcription factors play important roles in plant growth development, resistance and substance metabolism regulation. However, the exact function of the response to salt stress in plants with ...specific WRKY transcription factors remains unclear. In this research, we isolated a new WRKY transcription factor DgWRKY5 from chrysanthemum. DgWRKY5 contains two WRKY domains of WKKYGQK and two C
H
zinc fingers. The expression of DgWRKY5 in chrysanthemum was up-regulated under various treatments. Meanwhile, we observed higher expression levels in the leaves contrasted with other tissues. Under salt stress, the activities of superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT) enzymes in transgenic chrysanthemum were significantly higher than those in WT, whereas the accumulation of H
O
, O
and malondialdehyde (MDA) was reduced in transgenic chrysanthemum. Several parameters including root length, root length, fresh weight, chlorophyll content and leaf gas exchange parameters in transgenic chrysanthemum were much better compared with WT under salt stress. Moreover, the expression of stress-related genes DgAPX, DgCAT, DgNCED3A, DgNCED3B, DgCuZnSOD, DgP5CS, DgCSD1 and DgCSD2 was up-regulated in DgWRKY5 transgenic chrysanthemum compared with that in WT. These results suggested that DgWRKY5 could function as a positive regulator of salt stress in chrysanthemum.
The reasonable design and in-time optimisation of the supporting scheme is very important for ensuring the safe control of the surrounding rock. The key steps are to conduct in-situ real-time tests ...and quantitative evaluation of the surrounding rock before and after being supported. In order to solve the difficult problem of in-situ testing the surrounding rock, the surrounding rock digital drilling test system (SDT system) of underground engineering is developed, and the in-situ test and bolt-grouting design evaluation method of surrounding rock in underground engineering based on digital drilling is proposed. The systematic test studies including digital drilling test, borehole inspection and coring test are conducted on typical surrounding rock of chamber in the high stress mine of China. The effectiveness of SDT system and the prediction model of rock equivalent strength based on drilling applied to on-site engineering are validated. The zoning of surrounding rock of deep chamber based on equivalent strength is obtained, which are the strength deterioration zone, strength recovery zone and original rock strength zone, respectively. Based on the results of the in-situ digital drilling test of surrounding rock, the bolt-grouting support scheme to reinforce the surrounding rock is designed and evaluated. The average equivalent strength increase rate of the fractured regions of chamber surrounding rock reinforced by bolt-grouting is 61.6%. The bolt-grouting support can effectively enhance the strength of the fractured surrounding rock and reinforce the fractured rock mass. This study provides an effective means for classifying surrounding rock based on their strengths and design optimisation of the support system.
Chrysanthemum is one kind of ornamental plant well-known and widely used in the world. However, its quality and production were severely affected by low temperature conditions in winter and early ...spring periods. Therefore, we used the RNA-Seq platform to perform a de novo transcriptome assembly to analyze chrysanthemum (Dendranthema grandiflorum) transcription response to low temperature.
Using Illumina sequencing technology, a total of 86,444,237 high-quality clean reads and 93,837 unigenes were generated from four libraries: T01, controls; T02, 4 °C cold acclimation (CA) for 24 h; T03, - 4 °C freezing treatments for 4 h with prior CA; and T04, - 4 °C freezing treatments for 4 h without prior CA. In total, 7583 differentially expressed genes (DEGs) of 36,462 annotated unigenes were identified. We performed GO and KEGG pathway enrichment analyses, and excavated a group of important cold-responsive genes related to low temperature sensing and signal transduction, membrane lipid stability, reactive oxygen species (ROS) scavenging and osmoregulation. These genes encode many key proteins in plant biological processes, such as protein kinases, transcription factors, fatty acid desaturase, lipid-transfer proteins, antifreeze proteins, antioxidase and soluble sugars synthetases. We also verified expression levels of 10 DEGs using quantitative real-time polymerase chain reaction (qRT-PCR). In addition, we performed the determination of physiological indicators of chrysanthemum treated at low temperature, and the results were basically consistent with molecular sequencing results.
In summary, our study presents a genome-wide transcript profile of Dendranthema grandiflorum var. jinba and provides insights into the molecular mechanisms of D. grandiflorum in response to low temperature. These data contributes to our deeper relevant researches on cold tolerance and further exploring new candidate genes for chilling-tolerance and freezing-tolerance chrysanthemum molecular breeding.
Various types of broken rock masses, such as those in fault-fracture zones and fracture zones, which form as a result of disturbance from tunnelling, are often encountered during underground ...engineering construction. These rock masses have low self-supporting capacity and poor stability, which can easily cause damage to surrounding rock, such as large deformation features, collapse and falling blocks, etc., posing a threat to construction safety. During a field project, reinforcement by grouting is a primary means for addressing the aforementioned problems. The effective measurement of rock mass characteristics (e.g., rock layer interfaces and the broken area of surrounding rock) provides a basis for the reasonable design of a grouting scheme. The quantitative evaluation of the effect of rock mass grouting is essential for optimizing the grouting scheme. In view of this, in this study, a multi-functional rock mass digital drilling test system and a special polycrystalline diamond compact drill bit for digital testing were developed and were applied to conduct digital drilling tests on intact, broken and grouted rock masses. In addition, a digital drilling test (DDT) technique-based method for measuring rock mass characteristics in real time and rapidly evaluating the grouting effect was proposed. The proposed method is capable of identifying rock layer interfaces, determining the broken area and obtaining the equivalent strength of grouted rock masses. This method is advantageous for obtaining quantitative and rapid test results, which can provide a theoretical basis and technical means for optimizing the grouting parameters and designing support schemes for underground engineering construction.
Steerable hydrogen generation from the hydrogen storage chemical formic acid via heterogeneous catalysis has attracted considerable interest given the safety and efficiency concerns in handling H2. ...Herein, a series of carbon-supported capping-agent-free Pd nanoparticles (NPs) with mean sizes tunable from 2.0 to 5.2 nm are developed due to the demand for more efficient dehydrogenation from a formic acid–formate solution of pH 3.5 at room temperature. The trick for the facile size-controlled synthesis of Pd/C catalysts is the selective addition of Na2CO3, NH3·H2O, or NaOH to a Pd(II) solution to attain initial pH values of 7–9.5. For comparison, cuboctahedron modeling and electrochemical COads stripping methods are applied to evaluate active surface Pd sites for turnover frequency (TOF) calculation. Both mass activity and specific activity (TOF) of hydrogen production are not only time-dependent but also Pd-size-dependent. An initial H2 production rate of 246 L·h–1·gPd –1 is achieved on 2.0 nm Pd/C at 303 K, together with a TOF of 1815 h–1 on the basis of cuboctahedron modeling of surface-active Pd sites. The initial TOF exhibits a significant rise from 3.5 down to 2.8 nm and then levels off below 2.8 nm and even shows a maxima at ca. 2.2 nm using the electrochemical surface area for calculation. The volcano-shaped dependence of TOF on Pd NP size may be better attributed to the changing ratios of terrace sites to defect sites on Pd NPs.
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