Reversible Stacking of 2D ZnIn2 S4 Atomic Layers for Enhanced Photocatalytic Hydrogen Evolution.

It is technically challenging to reversibly tune the layer number of 2D materials in the solution. Herein, a facile concentration modulation strategy is demonstrated to reversibly tailor the aggregation state of 2D ZnIn2 S4 (ZIS) atomic layers, and they are implemented for effective photocatalytic hydrogen (H2 ) evolution. By adjusting the colloidal concentration of ZIS (ZIS-X, X = 0.09, 0.25, or 3.0 mg mL-1 ), ZIS atomic layers exhibit the significant aggregation of (006) facet stacking in the solution, leading to the bandgap shift from 3.21 to 2.66 eV. The colloidal stacked layers are further assembled into hollow microsphere after freeze-drying the solution into solid powders, which can be redispersed into colloidal solution with reversibility. The photocatalytic hydrogen evolution of ZIS-X colloids is evaluated, and the slightly aggregated ZIS-0.25 displays the enhanced photocatalytic H2 evolution rates (1.11 µmol m-2 h-1 ). The charge-transfer/recombination dynamics are characterized by time-resolved photoluminescence (TRPL) spectroscopy, and ZIS-0.25 displays the longest lifetime (5.55 µs), consistent with the best photocatalytic performance. This work provides a facile, consecutive, and reversible strategy for regulating the photo-electrochemical properties of 2D ZIS, which is beneficial for efficient solar energy conversion.

FIB-SEM combined with proteomics and modification omics clarified mechanisms of lipids synthesis in organelles of Chlorella pyrenoidosa cells with high CO2 concentration.

In order to explain reasons why flue-gas CO2 (normally containing high CO2) enhanced carbon fixation and lipids synthesis with increased photochemical electron production in microalgae cells. Focused ion beam scanning electron microscopy (FIB-SEM) was combined with proteomics and phosphorylation modification mics to clarify mechanisms of lipids synthesis at protein and organelle levels in Chlorella pyrenoidosa cells cultivated with high CO2 concentration (15 % v/v). The volumes of chloroplast and endoplasmic reticulum in subcellular organelles increased by 47 % and 306 %, respectively, compared with the control, which improved conversion efficiency of starch grains to lipids (lipid content increased by 57 %). Proteomics and modifications omics revealed that protein translation and ribosome structure and biogenesis-related enzymes were significantly modified by phosphorylation, which regulated protein biological functions. Glycolysis, pentose phosphate pathway and other carbohydrate metabolic pathways were markedly enriched and promoted the expression of lipid synthase, which was consistent with enhanced carbon fixation in photosynthesis, expansion of subcellular organelles and improved lipids synthesis.

Functional metabolism pathways of significantly regulated genes in Nannochloropsis oceanica with various nitrogen/phosphorus nutrients for CO2 fixation.

To determine the optimal CO2 concentration for microalgal biomass cultivated with industrial flue gas and improve carbon fixation capacity and biomass production. Functional metabolism pathways of significantly regulated genes in Nannochloropsis oceanica (N. oceanica) with various nitrogen/phosphorus (N/P) nutrients for CO2 fixation were comprehensively clarified. At 100 % N/P nutrients, the optimum CO2 concentration was 70 % and the maximum biomass production of microalgae was 1.57 g/L. The optimum CO2 concentration was 50 % for N or P deficiency and 30 % for both N and P deficiency. The optimal combination of CO2 concentration and N/P nutrients caused significant up regulation of proteins related to photosynthesis and cellular respiration in the microalgae, enhancing photosynthetic electron transfer efficiency and carbon metabolism. Microalgal cells with P deficiency and optimal CO2 concentration expressed many phosphate transporter proteins to enhance P metabolism and N metabolism to maintain a high carbon fixation capacity. However, inappropriate combination of N/P nutrients and CO2 concentrations caused more errors in DNA replication and protein synthesis, generating more lysosomes and phagosomes. This inhibited carbon fixation and biomass production in the microalgae with increased cell apoptosis.

Photodehydration of Ethanol Mediated by CuCl2-Ethanol Complex.

Biomass ethanol is regarded as a renewable resource but it is not economically viable to transform it to high-value industrial chemicals at present. Herein, a simple, green, and low-cost CuCl2-ethanol complex is reported for ethanol dehydration to produce ethylene and acetal simultaneously with high selectivity under sunlight irradiation. Under N2 atmosphere, the generation rates of ethylene and acetal were 165 and 3672 µmol g-1 h-1, accounting for 100% in gas products and 97% in liquid products, respectively. An outstanding apparent quantum yield of 13.2% (365 nm) and the maximum conversion rate of 32% were achieved. The dehydration reactions start from the photoexcited CuCl2-ethanol complex, and then go through the energy transfer (EnT) and ligand to metal charge transfer (LMCT) mechanisms to produce ethylene and acetal, respectively. The formation energies of the CuCl2-ethanol complex and the key intermediate radicals (e.g., ·OH, CH3CH2·, and CH3CH2O·) were validated to clarify the mechanisms. Different from previous CuCl2-based oxidation and addition reactions, this work is anticipated to supply new insights into the dehydration reaction of ethanol to produce useful chemical feedstocks.

CO2 gradient domestication improved high-concentration CO2 tolerance and photoautotrophic growth of Euglena gracilis.

In order to improve CO2 biofixation efficiency of microalgae cultivated with coal-chemical flue gas, CO2 gradient domestication was employed to improve high-concentration CO2 tolerance and photoautotrophic growth of acid-tolerant Euglena gracilis. The dried biomass yield of photoautotrophic growth of E.gracilis increased from 1.09 g/L (wild-type strain) by 21 % to 1.32 g/L with CO2 gradient domestication to 15 % CO2. The RuBisCO activity and biomass production of E.gracilis strain domesticated to 99 % CO2 were 2.63 and 3.4 times higher, respectively, than those of wild-type strain. The chlorophyll a and b contents were 2.52 and 1.79 times higher, respectively, than those of wild-type strain. Superoxide dismutase and catalase activities of 99 % CO2-domesticated strain increased to 1.24 and 6 times, which reduced peroxide damage under high carbon stress and resulted in lower apoptotic and necrotic rates of domesticated strain. Thus, this work provides valuable guidance for CO2 fixation and adaptive evolution of E. gracilis in industrial flue gas.

FIB-SEM analysis on three-dimensional structures of growing organelles in wild Chlorella pyrenoidosa cells.

To clarify dynamic changes of organelle microstructures in Chlorella pyrenoidosa cells during photosynthetic growth with CO2 fixation, three-dimensional (3D) organelle microstructures in three growth periods of meristem, elongation, and maturity were quantitatively determined and comprehensively reconstructed with focused ion beam scanning electron microscopy (FIB-SEM). The single round-pancake mitochondria in each cell split into a dumbbell and then into a circular ring, while the barycenter distance of mitochondria to chloroplast and nucleus was reduced to 45.5% and 88.3% to strengthen energy transfer, respectively. The single pyrenoid consisting of a large part and another small part in each chloroplast gradually developed to a mature state in which the two parts were nearly equal in size. The nucleolus progressively became larger with euchromatin replication. The number of starch grains gradually increased, but the mean grain volume remained nearly unchanged.

Impact of acceleration of agricultural and industrial waste conditioning on thermal drying of sewage sludge.

Improving the dewatering performance of sludge is a necessary advancement for collaborative sludge disposal and energy-efficient utilization in power plants. Herein, the effects of temperature changes and the addition of drying accelerators derived from agricultural and industrial waste on the drying characteristics of sewage sludge (SS) were investigated from the perspectives of drying kinetics and micromorphology. According to the results, the drying time for sludge significantly showed a clear downward trend via medium-low temperature (160 °C) thermal drying, which subsequently reduced the energy input substantially. When the drying temperature was 160 °C, the ideal addition proportions of rice husk (RH), sludge ash (SA), and coal ash (CA) comprised 15%. The addition of SA prominently boosted the drying rate constant of the original sludge by 48%. Additionally, SEM images along with the spectral dimension obtained via fractal theory explicitly clearly demonstrated that SS + SA had more loose pore channels than other mixed samples. This provided a convenient approach to ensure the evaporation and migration of moisture and thereby shorten the drying time effectively. Consequently, the addition of sludge ash as a drying accelerator can promote the deep dewatering of sludge.

Thermal pyrolysis of Si@ZIF-67 into Si@N-doped CNTs towards highly stable lithium storage.

Silicon is attracting considerable attention as an active anode material for advanced lithium-ion batteries due to its ultrahigh theoretical capacity. However, the reversible utilization of silicon-based anode materials is still hindered by the rapid capacity decay, as a consequence of the huge volume change of silicon during cycling. Herein, we use a Co-zeolitic imidazole framework (ZIF-67) to prepare silicon-wrapped nitrogen-doped carbon nanotubes (Si@N-doped CNTs) by controllable thermal pyrolysis. The as-prepared nanocomposites can effectively prevent pulverization and accommodate volume fluctuations of silicon during cycling. It can deliver a highly reversible capacity of 1100 mAh g-1 even after 750 cycles at a current density of 1000 mA g-1. As confirmed by an in situ transmission electron microscopy experiment, the remarkable electrochemical performance of Si@N-doped CNTs is attributed to the high electronic conductivity and flexibility of cross-linked N-doped CNTs network as a cushion to mitigate the mechanical stress and volume expansion. Furthermore, a full cell consisting of Si@N-doped CNTs anode and LiFePO4 cathode delivers a high reversible capacity of 1264 mAh g-1 and exhibits good cycling stability (>85% capacity retention) over 140 cycles at 1/4 C (1 C = 4000 mA g-1) rate.

Cu-MOF derived Cu-C nanocomposites towards high performance electrochemical supercapacitors.

For the development of asymmetric supercapacitors with higher energy density, the study of new electrode materials with high capacitance is a priority. Herein, the electrochemical behavior of nano copper in alkaline electrolyte is first discovered. It is found that there are two obvious reversible redox symmetric peaks in the range of -0.8-0.2 V in the alkaline electrolyte, corresponding to the conversion of copper into cuprous ions, and then converting cuprous ions into copper ions, indicating that the nanocomposite electrode has the characteristics of a pseudocapacitive reaction. It has a specific capacitance of up to 318 F g-1 at a current density of 1 A g-1, which remains at nearly 100% after 10 000 cycles at the same current density. When assembled with a Ni(OH)2-based electrode into an asymmetric supercapacitor, the device shows excellent capacitive behavior and good reaction reversibility. At 0.4 A g-1, the supercapacitor delivers a reversible capacity of 8.33 F g-1 with an energy density of 13.5 mW h g-1. This study first discovers the electrochemical behavior of nano copper, which can provide a new research idea for further expanding the negative electrodes of supercapacitors with higher energy density.

Tuning of Thermal Stability in Layered Li(NixMnyCoz)O2.

Understanding and further designing new layered Li(NixMnyCoz)O2 (NMC) (x + y + z = 1) materials with optimized thermal stability is important to rechargeable Li batteries (LIBs) for electrical vehicles (EV). Using ab initio calculations combined with experiments, we clarified how the thermal stability of NMC materials can be tuned by the most unstable oxygen, which is determined by the local coordination structure unit (LCSU) of oxygen (TM(Ni, Mn, Co)3-O-Li3-x'): each O atom bonds with three transition metals (TM) from the TM-layer and three to zero Li from fully discharged to charged states from the Li-layer. Under this model, how the lithium content, valence states of Ni, contents of Ni, Mn, and Co, and Ni/Li disorder to tune the thermal stability of NMC materials by affecting the sites, content, and the release temperature of the most unstable oxygen is proposed. The synergistic effect between Li vacancies and raised valence state of Ni during delithiation process can aggravate instability of oxygen, and oxygen coordinated with more nickel (especially with high valence state) in LSCU becomes more unstable at a fixed delithiation state. The Ni/Li mixing would decrease the thermal stability of the "Ni═Mn" group NMC materials but benefit the thermal stability of "Ni-rich" group, because the Ni in the Li layer would form 180° Ni-O-Ni super exchange chains in "Ni-rich" NMC materials. Mn and Co doping can tune the initial valence state of Ni, local coordination environment of oxygen, and the Ni/Li disorder, thus to tune the thermal stability directly.

Kinetics Tuning of Li-Ion Diffusion in Layered Li(NixMnyCoz)O2.

Using ab initio calculations combined with experiments, we clarified how the kinetics of Li-ion diffusion can be tuned in LiNixMnyCozO2 (NMC, x + y + z = 1) materials. It is found that Li-ions tend to choose oxygen dumbbell hopping (ODH) at the early stage of charging (delithiation), and tetrahedral site hopping (TSH) begins to dominate when more than 1/3 Li-ions are extracted. In both ODH and TSH, the Li-ions surrounded by nickel (especially with low valence state) are more likely to diffuse with low activation energy and form an advantageous path. The Li slab space, which also contributes to the effective diffusion barriers, is found to be closely associated with the delithiation process (Ni oxidation) and the contents of Ni, Co, and Mn.

SnS2 nanoparticle loaded graphene nanocomposites for superior energy storage.

SnS2 nanoparticle-loaded graphene nanocomposites were synthesized via one-step hydrothermal reaction. Their electrochemical performance was evaluated as the anode for rechargeable lithium-ion batteries after thermal treatment in an Ar environment. The electrochemical testing results show a high reversible capacity of more than 800 mA h g(-1) at 0.1 C rate and 200 mA h g(-1) for up to 5 C rate. The cells also exhibit excellent capacity retention for up to 90 cycles even at a high rate of 2 C. This electrochemical behavior can be attributed to the well-defined morphology and nanostructures of these as-synthesized nanocomposites, which is characterized by high-resolution transmission electron microscopy and electron energy-loss spectroscopy.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells.

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Here, we use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach enabled us to obtain a uniform and thin (around tens of nanometers) sulfur coating on graphene oxide sheets by a simple chemical reaction-deposition strategy and a subsequent low-temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides enabled us to demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mA h g(-1), and stable cycling for more than 50 deep cycles at 0.1C (1C = 1675 mA g(-1)).