Coupling methanol oxidation with CO2 reduction: A feasible pathway to achieve carbon neutralization.

The energy consumption of up to 90 % of the total power input in the anodic oxygen evolution reaction (OER) slows down the implementation of electrochemical CO2 reduction reaction (CO2RR) to generate valuable chemicals. Herein, we present an alternative strategy that utilizes methanol oxidation reaction (MOR) to replace OER. The iron single atom anchored on nitrogen-doped carbon support (Fe-N-C) use as the cathode catalyst (CO2RR), low-loading platinum supported on the composites of tungsten phosphide and multiwalled carbon nanotube (Pt-WP/MWCNT) use as the anode catalyst (MOR). Our results show that the Fe-N-C exhibits a Faradaic selectivity as high as 94.93 % towards CO2RR to CO, and Pt-WP/MWCNT exhibits a peak mass activity of 544.24 mA mg-1Pt, which is 5.58 times greater than that of PtC (97.50 mA mg-1Pt). The well-established MOR||CO2RR reduces the electricity consumption up to 52.4 % compared to conventional OER||CO2RR. Moreover, a CO2 emission analysis shows that this strategy not only saves energy but also achieves carbon neutrality without changing the existing power grid structure. Our findings have crucial implications for advancing CO2 utilization and lay the foundation for developing more efficient and sustainable technologies to address the rising atmospheric CO2 levels.

Roles of the SOM and clay minerals in alleviating the leaching of Pb, Zn, and Cd from the Pb/Zn smelter soil: Multi-surface model and DFT study.

Soil organic matter (SOM) and clay minerals are important sinks for reactive heavy metals (HMs) and exogenous hydrogen ions (H+). Therefore, HMs are likely to be released into soil porewater under acid rainfall conditions due to the competitive adsorption of H+. However, negligible Lead, Zinc, and Cadmium (<6 ‰) in the Pb/Zn smelter soil were leached, and the effects of SOM and clay minerals on HMs leaching were unclear. Herein, the H+ consumption and HMs redistribution on SOM and clay minerals were quantitated by the multi-surface model and density functional theory calculations to reveal the roles of SOM and clay minerals in alleviating HMs' leaching. Clay minerals consumed 43.2 %-52.0 % of the exogenous H+, serving as the dominant sink for the exogenous H+ due to its high content and hindering H+ competitive adsorption on SOM. Protonation of the functional groups constituted >90 % of the total H+ captured by clay minerals. Meanwhile, some H+ also competed with HMs for adsorption sites on clay minerals due to its 0.497-fold to 1.54-fold higher binding energies than HMs, resulting in the release of HMs. On the contrary, SOM served as an accommodator for taking over the released HMs from clay minerals. The HMs complexation on the low-affinity sites (R-L-) of SOM was responsible for the recapture of HMs. In Ca-enriched soil, the released HMs were also recaptured by SOM via ion exchange on the R-L-Ca+ and the high-affinity sites (R-H-Ca+) sites due to the 30.8 %-178 % higher binding energies of HMs on these sites than those of Ca. As a result, >63.4 % of the released HMs from clay minerals were transferred to the SOM. Thus, the synergy of SOM and clay minerals in alleviating the leaching of HMs in Pb/Zn smelter soils cannot be ignored in risk assessment and soil remediation.

Co-utilization of wastewater sludge and heavy metals for single-atom electrocatalytic reduction of gaseous CO2.

Synergetic management of waste activated sludge, heavy metals (HMs) and CO2 for their valorization and cyclic utilization is rarely reported. Herein, we employed sludge-derived extracellular polymeric substances (EPS) and HMs in wastewater to fabricate a gas diffusion electrode (GDE) for electrochemical CO2 reduction. This approach atomically dispersed Ni at each nanofiber of the GDE. Abundant N element in the EPS proved to play a key role in the formation of Nx-Ni (mixture of N3-Ni and N4-Ni) sites for highly efficient CO2 to CO conversion. The atomical Ni3+ shows high catalytic activity. Direct gaseous CO2 reduction in a membrane electrode assembly generated a current density up to 50 mA·cm-2 with CO:H2 ratio of ∼100 and ∼75% FECO under 2.69 cell voltage. This strategy takes advantage of all waste streams generated on site and consolidates traditionally separated treatment processes to save costs, produces value-added products and generates carbon benefits during wastewater treatment.

The roles of typical emerging pollutants on N2O emissions during biological nitrogen removal from wastewater.

N2O as a potent greenhouse gas often generates in the biological nitrogen removal (BNR) processes during wastewater treatment, which makes BNR become an important greenhouse gas emission source. The emerging pollutants (EPs) are ubiquitous in wastewater and they have shown to influence the BNR processes. However, the deep discussion on potential impacts of EPs on N2O emissions during BNR is rare. Moreover, the experimental parameters for EPs investigation in most of literatures are generally not in line with real-world BNR processes, which calls for deep elucidating the roles of EPs on N2O production and emission. In this work, a critical review summarizes the existing literature about influences of typical EPs on N2O emissions and associated mechanisms during BNR, and it discusses the impacts of some easily overlooked factors, such as real EPs environmental concentrations, EPs bioaccumulation, and multiple EPs coexistence on N2O emissions. This review will provide an insight into exploring and mitigating threats posed by typical EPs on N2O emissions.

A Hybrid Soft Sensor Model for Measuring the Oxygen Content in Boiler Flue Gas.

As an indispensable component of coal-fired power plants, boilers play a crucial role in converting water into high-pressure steam. The oxygen content in the flue gas is a crucial indicator, which indicates the state of combustion within the boiler. The oxygen content not only affects the thermal efficiency of the boiler and the energy utilization of the generator unit, but also has adverse impacts on the environment. Therefore, accurate measurement of the flue gas's oxygen content is of paramount importance in enhancing the energy utilization efficiency of coal-fired power plants and reducing the emissions of waste gas and pollutants. This study proposes a prediction model for the oxygen content in the flue gas that combines the whale optimization algorithm (WOA) and long short-term memory (LSTM) networks. Among them, the whale optimization algorithm (WOA) was used to optimize the learning rate, the number of hidden layers, and the regularization coefficients of the long short-term memory (LSTM). The data used in this study were obtained from a 350 MW power generation unit in a coal-fired power plant to validate the practicality and effectiveness of the proposed hybrid model. The simulation results demonstrated that the whale optimization algorithm-long short-term memory (WOA-LSTM) model achieved an MAE of 0.16493, an RMSE of 0.12712, an MAPE of 2.2254%, and an R2 value of 0.98664. The whale optimization algorithm-long short-term memory (WOA-LSTM) model demonstrated enhancements in accuracy compared with the least squares support vector machine (LSSVM), long short-term memory (LSTM), particle swarm optimization-least squares support vector machine (PSO-LSSVM), and particle swarm optimization-long short-term memory (PSO-LSTM), with improvements of 4.93%, 4.03%, 1.35%, and 0.49%, respectively. These results indicated that the proposed soft sensor model exhibited more accurate performance, which can meet practical requirements of coal-fired power plants.

Artificial Soil-Like Material Enhances CO2 Bio-Valorization into Chemicals in Gas Fermentation.

Gas fermentation offers a carbon-neutral route for producing industrial feedstocks using autotrophic microbes to convert carbon dioxide (CO2) in waste gases, such as industrial emissions and biogas, into valuable chemicals or biofuels. However, slow microbial metabolism owing to low gaseous solubility causes significant challenges in gas fermentation. Although chemical or genetic manipulations have been explored to improve gas fermentation, they are either nonsustainable or complex. Herein, an artificial soil-like material (SLM) inspired by natural soil was fabricated to improve the growth and metabolism ofCupriavidus necatorfor enhanced poly-ß-hydroxybutyrate (PHB) biosynthesis from CO2 and hydrogen (H2). Porous SLM comprises low-cost nanoclay, boehmite, and starch and serves as a biocarrier to facilitate the colonization of bacteria and delivery of CO2 to bacteria. With 3.0 g/L SLM addition, the solubility of CO2 in water increased by ∼4 times and biomass and PHB production boosted by 29 and 102%, respectively, in the 24 h culture. In addition, a positive modulation was observed in the metabolism of PHB biosynthesis. PHB biosynthesis-associated gene expression was found to be enhanced in response to the SLM addition. The concentrations of intermediates in the metabolic pathway of PHB biosynthesis, such as pyruvate and acetyl-CoA, as well as reducing energy (ATP and NADPH) significantly increased with SLM addition. SLM also demonstrated the merits of easy fabrication, high stability, recyclability, and plasticity, thereby indicating its considerable potential for large-scale application in gas fermentation.

Bi Nanosheets on Porous Carbon Cloth Composites for Ultrastable Flexible Nickel-Bismuth Batteries.

The use of bismuth (Bi) as an anode material in nickel-metal batteries has gained significant attention due to its highly reversible redox reaction and suitable operating conditions. However, the cycling stability and flexibility of nickel-bismuth (Ni//Bi) batteries need to be further improved. This paper employs a facile electrodeposition technique to prepare Bi nanosheets uniformly grown on a porous carbon cloth (PCC), denoted as Bi-PCC electrodes. The Bi-PCC electrode portrays a specific surface area and good wettability that enable fast charge transfer and ion transport channels. Consequently, the Bi-PCC electrode demonstrates a high specific capacity of up to 297.1 mAh g-1 at 2 A g-1, with a capacity retention of up to 71.5% at 2-40 A g-1 and an impressive capacity retention of 79.9% after 1000 cycles at 2-40 A g-1. More importantly, the flexible rechargeable Ni//Bi battery (denoted as Ni(OH)2-PCC//Bi-PCC) with Bi-PCC as the anode and Ni(OH)2-PCC as the cathode has excellent electrochemical performance. The Ni(OH)2-PCC//Bi-PCC battery boasts a remarkable capacity retention of 93.6% after 3000 cycles at 10 A g-1. Further, the cell presents a maximum energy density of 73.1 Wh kg-1 and an impressive power density of 11.9 kW kg-1.

Zinc Single Atom Confinement Effects on Catalysis in 1T-Phase Molybdenum Disulfide.

Active sites are atomic sites within catalysts that drive reactions and are essential for catalysis. Spatially confining guest metals within active site microenvironments has been predicted to improve catalytic activity by altering the electronic states of active sites. Using the hydrogen evolution reaction (HER) as a model reaction, we show that intercalating zinc single atoms between layers of 1T-MoS2 (Zn SAs/1T-MoS2) enhances HER performance by decreasing the overpotential, charge transfer resistance, and kinetic barrier. The confined Zn atoms tetrahedrally coordinate to basal sulfur (S) atoms and expand the interlayer spacing of 1T-MoS2 by ∼3.4%. Under confinement, the Zn SAs donate electrons to coordinated S atoms, which lowers the free energy barrier of H* adsorption-desorption and enhances HER kinetics. In this work, which is applicable to all types of catalytic reactions and layered materials, HER performance is enhanced by controlling the coordination geometry and electronic states of transition metals confined within active-site microenvironments.

Evolutionary analysis and lineage designation of SARS-CoV-2 genomes.

The pandemic due to the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the etiological agent of coronavirus disease 2019 (COVID-19), has caused immense global disruption. With the rapid accumulation of SARS-CoV-2 genome sequences, however, thousands of genomic variants of SARS-CoV-2 are now publicly available. To improve the tracing of the viral genomes' evolution during the development of the pandemic, we analyzed single nucleotide variants (SNVs) in 121,618 high-quality SARS-CoV-2 genomes. We divided these viral genomes into two major lineages (L and S) based on variants at sites 8782 and 28144, and further divided the L lineage into two major sublineages (L1 and L2) using SNVs at sites 3037, 14408, and 23403. Subsequently, we categorized them into 130 sublineages (37 in S, 35 in L1, and 58 in L2) based on marker SNVs at 201 additional genomic sites. This lineage/sublineage designation system has a hierarchical structure and reflects the relatedness among the subclades of the major lineages. We also provide a companion website (www.covid19evolution.net) that allows users to visualize sublineage information and upload their own SARS-CoV-2 genomes for sublineage classification. Finally, we discussed the possible roles of compensatory mutations and natural selection during SARS-CoV-2's evolution. These efforts will improve our understanding of the temporal and spatial dynamics of SARS-CoV-2's genome evolution.

Dynamic evolution and reversibility of single-atom Ni(II) active site in 1T-MoS2 electrocatalysts for hydrogen evolution.

1T-MoS2 and single-atom modified analogues represent a highly promising class of low-cost catalysts for hydrogen evolution reaction (HER). However, the role of single atoms, either as active species or promoters, remains vague despite its essentiality toward more efficient HER. In this work, we report the unambiguous identification of Ni single atom as key active sites in the basal plane of 1T-MoS2 (Ni@1T-MoS2) that result in efficient HER performance. The intermediate structure of this Ni active site under catalytic conditions was captured by in situ X-ray absorption spectroscopy, where a reversible metallic Ni species (Ni0) is observed in alkaline conditions whereas Ni remains in its local structure under acidic conditions. These insights provide crucial mechanistic understanding of Ni@1T-MoS2 HER electrocatalysts and suggest that the understanding gained from such in situ studies is necessary toward the development of highly efficient single-atom decorated 1T-MoS2 electrocatalysts.

Size-Dependent Nickel-Based Electrocatalysts for Selective CO2 Reduction.

Closing the anthropogenic carbon cycle by converting CO2 into reusable chemicals is an attractive solution to mitigate rising concentrations of CO2 in the atmosphere. Herein, we prepared Ni metal catalysts ranging in size from single atoms to over 100 nm and distributed them across N-doped carbon substrates which were obtained from converted zeolitic imidazolate frameworks (ZIF). The results show variance in CO2 reduction performance with variance in Ni metal size. Ni single atoms demonstrate a superior Faradaic efficiency (FE) for CO selectivity (ca. 97 % at -0.8 V vs. RHE), while results for 4.1 nm Ni nanoparticles are slightly lower (ca. 93 %). Further increase the Ni particle size to 37.2 nm allows the H2 evolution reaction (HER) to compete with the CO2 reduction reaction (CO2 RR). The FE towards CO production decreases to under 30 % and HER efficiency increase to over 70 %. These results show a size-dependent CO2 reduction for various sizes of Ni metal catalysts.

Photo/Bio-Electrochemical Systems for Environmental Remediation and Energy Harvesting.

Water and energy systems are interdependent: water is utilized in each stage of energy production, and energy is required to extract, treat, and deliver water for many uses. However, energy and water systems are usually developed and managed independently. In the quest to develop environmentally friendly and energy-efficient solutions for water and energy issues, photoelectrochemical (PEC) energy conversion and microbial electrochemical (MEC) systems show profound potential for addressing environmental remediation problems and harvesting energy simultaneously. Herein, PEC, MEC, and their variant hybrid systems toward energy conversion and environmental remediation are summarized and discussed.

Mannich Base as Corrosion Inhibitors for N80 Steel in a CO2 Saturated Solution Containing 3 wt % NaCl.

In this paper, a corrosion inhibitor containing nitrogen atoms and a conjugated π bond was synthesised, and its final product synthesised by the optimal conditions of the orthogonal test results is named multi-mannich base (MBT). The corrosion inhibition effect on the N80 steel sheet of the corrosion inhibitor was evaluated in a CO2 saturated solution containing 3 wt % NaCl; the corrosion rate was 0.0446 mm/a and the corrosion inhibition rate was 90.4%. Through electrochemical and adsorption theory study, MBT is a mixed corrosion inhibitor that mainly shows cathode suppression capacity. The adsorption of MBT on the surface of the steel sheet follows the Langmuir adsorption isotherm; it can be spontaneously adsorbed on the surface of the N80 steel sheet, which has a good corrosion inhibition effect. The surface of the N80 steel sheet was microscopically characterised by atomic force microscope (AFM). It can be seen from the results that the N80 steel sheet with MBT added is significantly different from the blank control group; the surface of the steel sheet is relatively smooth, indicating that MBT forms an effective protective film on the surface of N80 steel, which inhibits the steel sheet.

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

Functional study on baculovirus anti-apoptosis genes.

Apoptosis of bollworm cell line Hz-AM1 can be delayed by transient expression of AcNPV (Autographa californica Nuclear Polihedrosis Virus) p35 gene. Acp35Z, a p35 inactivated AcNPV by inserting with LacZ gene, cannot replicate in Hz-AM1 cells. However, the replication can be rescued by co-transfection with a plasmid containing AcNPV p35 gene. It is also realized that the transient expression of AcNPV p35 gene in Hela cells can put off cell apoptosis which is induced by adding actinomycin-D. Through co-transfection and G418 screening, two anti-apoptosis cell lines named Sf9-35 and Vero-35 are established by integrating AcNPV p35 and Neo expression cassette into the cell chromosomes. The Sf9-35 enhances the yield of budded virus of AcNPV, while the Vero-35 increases the propagation of measles virus.

Induction of Apoptosis in Tumor Cells by a Recombinant Adenovirus with bak Gene.

Apoptosis, a genetically encoded process of cellular suicide, comprises an intrinsic cellular defence against tumorigenesis. bak(for bcl-2 homologous antagonist/killer) is a new apoptosis-inducing gene found recently, which is identified in all tissues examined. Initial work of Farrow, Chittenden and Klefer indicated that bak plays an important role in apoptosis. Successive work of others suggests inactivity of Bak always accompanies the development of tumor cells. In this work, a shuttle vector harboring bak gene, pCA13-bak, was constructed and used to cotransfect into the cell line 293 together with a recombinant plasmid, pBHG11, containing most of adenovirus genome. A mutant adenovirus(delete E1, E3 region)carring bak, Ad-bak, was obtained, and purified. Dot blot identified the construction of recombinant virus was successful. HeLa cells were infected by this virus. Some manners were used to identify the changes of HeLa cells including Annexin V-FITC staining which made the reversed PS observed directly, microscope observation and others. The characteristic morphology of apoptotic cells was due to Ad-bak. The experiment suggests that bak is a strong apoptosis-inducing gene, and a potential gene which could be used in gene therapy on tumor.