Atmospheric chemistry of 2-nitrobenzaldehyde:Initiated by photo-excitation,OH-oxidation,and small TiO_(2) clusters adsorption catalysis

The fate of 2-nitrobenzaldehyde(2-NBA)is of interest in atmospheric chemistry as it is a semi-volatile organic compound with high photosensitivity.This study presents a quantum chemical study of the gas-phase reactions of 2-NBA photo-excitation and OH-oxidation in the absence and presence of small TiO_(2) clusters.To further understand the unknown photolysis mechanism,the photo-reaction pathways of ground singlet state and the lying excited triplet state of 2-NBA were investigated including the initial and subsequent reactions of proton transfer,direct CO,NO_(2),and HCO elimination routes in the presence of O_(2) and NO.Meanwhile,the OH-mediated degradation of 2-NBA proceeded via five H-extraction and six OH-addition channels by indirect mechanism,which follows a succession of reaction steps initiated by the formation of weakly stable intermediate complexes.The H-extraction from the-CHO group was the dominant pathway with a negative activation energy of-1.22 kcal/mol.The calculated rate coefficients at 200–600 K were close to the experimental data in literature within 308-352 K,and the kinetic negative temperature independence was found in both experimental literature and computational results.Interestingly,2-NBA was favored to be captured onto small TiO_(2) clusters via six adsorption configurations formed via various combination of three types of bonds of Ti…O,Ti…C,and O…H between the molecularly adsorbed 2-NBA and TiO_(2) clusters.Comparison indicted that the chemisorptions of aldehyde oxygen have largest energies.The results suggested adsorption conformations have a respectable impact on the catalysis barrier.This study is significant for understanding the atmospheric chemistry of 2-nitrobenzaldehyde.

Polysulfides adsorption and catalysis dual-sites on metal-doped molybdenum oxide nanoclusters for Li-S batteries with wide operating temperature

The development of electrocatalysts with high catalytic activity is conducive to enhancing polysulfides adsorption and reducing activation energy of polysulfides conversion, which can effectively reduce polysulfide shuttling in Li-S batteries. Herein, a novel catalyst NiCo-MoO x /rGO (rGO = reduced graphene oxides) with ultra-nanometer scale and high dispersity is derived from the Anderson-type polyoxometalate precursors, which are electrostatically assembled on the multilayer rGO. The catalyst material possesses dual active sites, in which Ni-doped MoO x exhibits strong polysulfide anchoring ability, while Co-doped MoO x facilitates the polysulfides conversion reaction kinetics, thus breaking the Sabatier effect in the conventional electrocatalytic process. In addition, the prepared NiCo-MoO x /rGO modified PP separator (NiCo-MoO x /rGO@PP) can serve as a physical barrier to further inhibit the polysulfide shuttling effect and realize the rapid Li+ migration. The results demonstrate that Li-S coin cell with NiCo-MoO x /rGO@PP separator shows excellent cycling performance with the discharge capacity of 680 mAh·g^(−1) after 600 cycles at 1 C and the capacity fading of 0.064% per cycle. The rate performance is also impressive with the remained capacity of 640 mAh·g^(−1) after 200 cycles even at 4 C. When the sulfur loading is 4.0 mg·cm^(−2) and electrolyte volume/sulfur mass ratio (E/S) ratio is 6.0 μL·mg^(−1), a specific capacity of 830 mAh·g^(−1) is achieved after 200 cycles with a capacity decay of 0.049% per cycle. More importantly, the cell with NiCo-MoO x /rGO@PP separator exhibits cycling performance under wide operating temperature with the reversible capacities of 518, 715, and 915 mAh·g^(−1) after 100 cycles at −20, 0, and 60 °C, respectively. This study provides a new design approach of highly efficient catalysts for sulfur conversion reaction in Li-S batteries.

Bimetallic Ni-Co MOF@PAN modified electrospun separator enhances high-performance lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with high energy density are considered promising energy storage devices for the next generation.Nevertheless,the shuttle effect and the passive layer between the separator and the electrodes still seriously affect the cycle stability and life.Herein,a bimetallic Ni-Co metal-organic framework(MOF)with adsorption and catalytic synergism for polysulfides was successfully synthesized as an electrospinning separator sandwich for Li-S batteries.Introducing porous Ni-Co MOF coatings into the separator provides more adsorption catalytic sites for polysulfides,prevents their diffusion to the anode,and enhances sulfur utilization.Consequently,the improved Li-S batteries with a Ni-Co MOF@PAN(NCMP)electrospun separator delivered excellent rate performance and outstanding cycle stability,yielding an ultra-high initial capacity of 1560 mA h g^(-1)at 0.1 C.Notably,remarkable Li-S battery performance with a discharge capacity of 794 mA h g^(-1)(84.1%capacity retention)was obtained after500 cycles,while delivering a low capacity decay rate of 0.032%during long-term cycling(up to 500cycles)at 1 C.Surprisingly,even at the current density of 2 C,the capacity attenuation rate of 2000 cycles is only 0.034%per cycle.In addition,compared with the Celgard separator,the NCMP separator also had high thermal stability(keeping the separator outline at 200℃)that ensured battery safety and excellent electrolyte wettability(73%porosity and 535%electrolyte absorption)and significantly enhanced the ionic conductivity and Li^(+) transfer number,and protected the surface integrity of the anode.

Tetracycline removal via adsorption and metal-free catalysis with 3D macroscopic N-doped porous carbon nanosheets:Non-radical mechanism and degradation pathway

Recently,metal-based carbon materials have been verified to be an effective persulfate activator,but secondary pollution caused by metal leaching is inevitable.Hence,a green metalfree 3D macroscopic N-doped porous carbon nanosheets(NPCN)was synthesized successfully.The obtained NPCN showed high adsorption capacity of tetracycline(TC)and excellent persulfate(PS)activation ability,especially when calcined at 700℃(NPCN-700).The maximum adsorption capacity of NPCN-700 was 121.51 mg/g by H-bonds interactions.Moreover,the adsorption process followed pseudo-second-order kinetics model and Langmuir adsorption isotherm.The large specific surface area(365.27 mg/g)and hierarchical porous structure of NPCN-700 reduced the mass transfer resistance and increased the adsorption capacity.About 96.39%of TC was removed after adding PS.The effective adsorption of the catalyst greatly shortened the time for the target organic molecules to migrate to the catalyst.Moreover,the NPCN-700 demonstrated high reusability with the TC removal rate of 80.23%after 4 cycles.Quenching experiment and electron paramagnetic resonance(EPR)test confirmed the non-radical mechanism dominated by ^(1)O_(2).More importantly,the C=O groups,defects and Graphitic N acted as active sites to generate ^(1)O_(2).Correspondingly,electrochemical measurement revealed the direct electron transfer pathway of TC degradation.Finally,multiple degradation intermediates were recognized by the LC-MS measurement and three possible degradation pathways were proposed.Overall,the prepared NPCN had excellent application prospects for removal of antibiotics due to its remarkable adsorption and catalytic degradation capabilities.

MOFs derived ZnSe/N-doped carbon nanosheets as multifunctional interlayers for ultralong-Life lithium-sulfur batteries

The shuttle effect and slow conversion rate of lithium polysulfides(LiPSs)have become the main obstructs to the development of lithium-sulfur(Li-S)batteries.Herein,the low cost metal-organic frameworks derived nitrogen-doped carbon nanosheets embedded with zinc selenide nanoparticles(ZnSe/NC nanosheets)were designed and synthesized for Li-S batteries.As the LiPSs trapping-layer,these nanocomposites provide some key benefits:(1)The nitrogen doping changes local electron distribution in the carbon nanosheets,thus the electrical conductivity is greatly improved for facilitating the transport of electrons/ions.(2)Nitrogen atoms and ZnSe nanoparticles play an important role in anchoring the LiPSs via chemical interactions.(3)The remarkable catalytic activity of ZnSe nanoparticles can accelerate the redox kinetics of LiPSs.As a result,the Li-S battery with the ZnSe/NC nanosheets modified separator exhibits ultralong lifespan over 1500 cycles with a small capacity loss of only 0.046%per cycle at 1 C,which is superior over those reported values.Furthermore,the Li-S battery with a high sulfur loading of 4.71 mg cm^(-2) can still maintain a high areal capacity of 4.28 mAh cm^(-2) after 50 cycles.This work provides a new route to the design of multifunctional low cost and high-performance separators for remarkably stable Li-S batteries.