Concentrated Formic Acid from CO2 Electrolysis for Directly Driving Fuel Cell.

The production of formic acid via electrochemical CO2 reduction may serve as a key link for the carbon cycle in the formic acid economy, yet its practical feasibility is largely limited by the quantity and concentration of the product. Here we demonstrate continuous electrochemical CO2 reduction for formic acid production at 2 M at an industrial-level current densities (i.e., 200 mA cm-2 ) for 300 h on membrane electrode assembly using scalable lattice-distorted bismuth catalysts. The optimized catalysts also enable a Faradaic efficiency for formate of 94.2 % and a highest partial formate current density of 1.16 A cm-2 , reaching a production rate of 21.7 mmol cm-2 h-1 . To assess the practicality of this system, we perform a comprehensive techno-economic analysis and life cycle assessment, showing that our approach can potentially substitute conventional methyl formate hydrolysis for industrial formic acid production. Furthermore, the resultant formic acid serves as direct fuel for air-breathing formic acid fuel cells, boasting a power density of 55 mW cm-2 and an exceptional thermal efficiency of 20.1 %.

EQNAS: Evolutionary Quantum Neural Architecture Search for Image Classification.

Quantum neural network (QNN) is a neural network model based on the principles of quantum mechanics. The advantages of faster computing speed, higher memory capacity, smaller network size and elimination of catastrophic amnesia make it a new idea to solve the problem of training massive data that is difficult for classical neural networks. However, the quantum circuit of QNN are artificially designed with high circuit complexity and low precision in classification tasks. In this paper, a neural architecture search method EQNAS is proposed to improve QNN. First, initializing the quantum population after image quantum encoding. The next step is observing the quantum population and evaluating the fitness. The last is updating the quantum population. Quantum rotation gate update, quantum circuit construction and entirety interference crossover are specific operations. The last two steps need to be carried out iteratively until a satisfactory fitness is achieved. After a lot of experiments on the searched quantum neural networks, the feasibility and effectiveness of the algorithm proposed in this paper are proved, and the searched QNN is obviously better than the original algorithm. The classification accuracy on the mnist dataset and the warship dataset not only increased by 5.31% and 4.52%, respectively, but also reduced the parameters by 21.88% and 31.25% respectively. Code will be available at https://gitee.com/Pcyslist/models/tree/master/research/cv/EQNAS, and https://github.com/Pcyslist/EQNAS.

Effect of acid treatment on boosting the photoelectrochemical performance of doped and codoped α-Fe2O3 photoanodes.

Acid treatment of Ti-doped α-Fe2O3 photoanode can reduce the onset potential and promote the photocurrent density for photoelectrochemical (PEC) water splitting reaction. However, the inner mechanism of how this occurs has not yet been clarified. This report compares the effect of HCl hydrothermal treatment on α-Fe2O3 photoanodes doped with Ge, Pt, Ti, and Sn or codoped with TiGe, TiPt, and TiSn. The findings show that the promotion effect of HCl hydrothermal treatment was far less significant on the Ge-, Pt-, and Sn-doped α-Fe2O3 than on the Ti-doped one. In contrast, the codoped photoanodes could realize a lift in the photocurrent of up to 39% at 1.23 VRHE (versus the reversible hydrogen electrode) and a reduction in the potential onset by ∼60 mV after HCl hydrothermal treatment. Anatase TiO2 was detected by Raman spectroscopy on the Ti-doped α-Fe2O3 with adequate treatment in HCl solution. Thus, the performance promotion by acid treatment was ascribed to the surface-concentrated Ti-O bonds acting as a passivation layer that could increase the charge-capture capacity and reduce the charge-transfer resistance, as demonstrated by the potential-modulated electrochemical impedance spectroscopy results. HCl treatment of the in situ-doped α-Fe2O3 and an excessive treatment time for the ex situ-doped α-Fe2O3 caused an inhibition in the PEC performance, which could be attributed to the adverse effect of lattice defects induced by acid corrosion. The application scope of HCl treatment on the doped α-Fe2O3 was determined by revealing its working mechanism.

NMDARs antagonist MK801 suppresses LPS-induced apoptosis and mitochondrial dysfunction by regulating subunits of NMDARs via the CaM/CaMKII/ERK pathway.

Lipopolysaccharide (LPS) displays a robust immunostimulatory ability upon Toll-like receptor 4 (TLR4) recognition. N-methyl-D-aspartate receptors (NMDARs) are highly compartmentalized in most cells and implicated in various inflammatory disorders. However, the relationship between TLR4 and NMDARs has not been explored deeply. This study aimed to examine the role of NMDARs and its specific inhibitor MK801 in LPS-treated endothelial cell dysfunction and the related mechanism in vivo and in vitro. The results showed that pre-treatment with MK801 significantly decreased LPS-induced cell death, cellular Ca2+, cellular reactive oxygen species, and glutamate efflux. Moreover, MK801 restrained LPS-induced mitochondrial dysfunction by regulating mitochondrial membrane potential and mitochondrial Ca2+ uptake. The oxygen consumption, basal and maximal respiration rate, and ATP production in LPS-treated HUVECs were reversed by MK801 via regulating ATP synthesis-related protein SDHB2, MTCO1, and ATP5A. The molecular pathway involved in MK801-regulated LPS injury was mediated by phosphorylation of CaMKII and ERK and the expression of MCU, MCUR1, and TLR4. LPS-decreased permeability in HUVECs was improved by MK801 via the Erk/ZO-1/occluding/Cx43 axis. Co-immunoprecipitation assay and western blotting showed three subtypes of NMDARs, NMDAζ1, NMDAε2, and NMDAε4 were bound explicitly to TLR4, suppressed by LPS, and promoted by MK801. Deficiency of NMDAζ1, NMDAε2, or NMDAε4 induced cell apoptosis, Ca2+ uptake, ROS production, and decreased basal and maximal respiration rate, and ATP production, suggesting that NMDARs integrity is vital for cell and mitochondrial function. In vivo investigation showed MK801 improved impairment of vascular permeability, especially in the lung and mesentery in LPS-injured mice. Our study displayed a novel mechanism and utilization of MK801 in LPS-induced ECs injury and permeability.

Potential metabolomic biomarkers for the identification and diagnosis of type A acute aortic dissection in patients with hypertension.

Objectives: Most patients with acute aortic dissection (AAD) have a history of hypertension. Diagnosis of AAD in patients with hypertension at an early stage is complicated and challenging. This study aimed to explore the distinctive metabolic changes in plasma samples of AAD patients with hypertension and patients with hypertension only and provide early identification and diagnosis of AAD in patients with hypertension. Materials and methods: We collected blood samples from 20 patients with type A AAD and hypertension admitted to the emergency department and physically examined other 20 patients with hypertension as controls. The plasma metabolomic profiles of these patients were determined using untargeted metabolomics with ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Results: A total of 38 metabolites that differed between the AAD and hypertension groups were screened. In the positive ion mode, 12 metabolites were different between the two groups, and in the negative ion mode, 26 metabolites were different. Among the 26 different metabolites detected by the negative ion mode, 21 were significantly upregulated and five were downregulated in patients with AAD compared to patients with hypertension. Moreover, five metabolites were upregulated and seven were significantly downregulated in patients with AAD compared to those with hypertension, as detected by the positive ion mode. The metabolites differentially expressed in AAD were mainly involved in lipid metabolism (fatty acid biosynthesis, biosynthesis of unsaturated fatty acids, and linoleic acid metabolism), carbohydrate metabolism (galactose, fructose, and mannose metabolisms), and membrane transport (ATP-binding cassette transporters). Interestingly, plasma hydrocortisone and dimethylglycine concentrations were significantly increased in patients with type A AAD, with the highest area under the curve value (AUC = 0.9325 or 0.9200, respectively) tested by the receiver operating characteristic curve analysis. Conclusion: This study provides possible metabolic markers for the early clinical diagnosis of AAD in patients with hypertension.

Constructing Reactive Micro-Environment in Basal Plane of MoS2 for pH-Universal Hydrogen Evolution Catalysis.

MoS2 represents a promising catalyst for the hydrogen evolution reaction (HER) in water splitting, but the inefficient catalytic activity in a pH-universal environment is an obstacle to developing practical applications. Boosting and balancing the water dissociation and hydrogen desorption kinetics is crucial in designing high-performance catalysts for the overall pH range. Herein, it is experimentally demonstrated that cobalt single-atom doping can effectively construct a reactive CoMoS micro-environment on the basal plane of MoS2 and thus alter the uniformity of surface electron density, which is further confirmed by the theoretical results. The reactive micro-environment consisting of single-atom Co with the surrounding Mo and S atoms possesses excellent water dissociation and hydrogen desorption kinetics, exhibiting a superior performance of 36 mV at 10 mA cm-2 with a Tafel slope of 33 mV dec-1 in the alkaline condition. Meanwhile, it also shows worthy activity in the acidic (97 mV) and neutral (117 mV) environments. This work provides a facile strategy to improve the HER catalysis of MoS2 in pH-universal environments.

Cu2O-Ag Tandem Catalysts for Selective Electrochemical Reduction of CO2 to C2 Products.

The electrochemical carbon dioxide reduction reaction (CO2RR) to C2 chemicals has received great attention. Here, we report the cuprous oxide (Cu2O) nanocubes cooperated with silver (Ag) nanoparticles via the replacement reaction for a synergetic CO2RR. The Cu2O-Ag tandem catalyst exhibits an impressive Faradaic efficiency (FE) of 72.85% for C2 products with a partial current density of 243.32 mA·cm-2. The electrochemical experiments and density functional theory (DFT) calculations reveal that the introduction of Ag improves the intermediate CO concentration on the catalyst surface and meanwhile reduces the C-C coupling reaction barrier energy, which is favorable for the synthesis of C2 products.

Insight into both coverage and surface structure dependent CO adsorption and activation on different Ni surfaces from DFT and atomistic thermodynamics.

CO adsorption and activation on Ni(100), (110) and (111) surfaces have been systematically investigated to probe the effect of coverage and surface structure on CO adsorption and activation. Herein, dispersion-corrected density functional theory calculations (DFT-D) were employed, and the related thermodynamic energies at 523 K were calculated by including the zero-point energy, thermal energy and entropic corrections; the results show that the saturated coverage of CO on the Ni(111), (100) and (110) surfaces correspond to 8/9, 9/12 and 9/9 ML, respectively. As the coverage increases, the stepwise adsorption free energies decrease on the flat (111) and (100) surfaces, whereas small changes occur on the corrugated (110) surface. CO migrates from the three-fold hollow site to the top site on the (111) surface, and from the four-fold hollow to the two-fold bridge site on the (100) surface, while all the CO molecules remain at the short-bridge site on the (110) surface. As a result, the obtained intermolecular CO-CO repulsive interactions on the flat surface are stronger than the interactions on the corrugated surface. Furthermore, the computed CO vibrational frequencies at different levels of coverage over the Ni surfaces agree well with the experimental results. On the other hand, kinetic analyses were utilized to compare the stepwise CO desorption with the dissociation at different degrees of coverage on the three Ni surfaces. CO desorption is more favorable than its dissociation at all coverage levels on the most exposed Ni(111) surface. Analogously, CO desorption becomes more favorable than its dissociation on the Ni(110) surface at higher coverage, except for coverage of 1/9 ML, in which CO desorption competes with its dissociation. However, on the Ni(100) surface, CO dissociation is more favorable than its desorption at 1/12 ML; when the coverage increases from 2/12 to 3/12 ML, equilibrium states exist between dissociation and desorption over the surface; when the coverage is greater than or equal to 4/9 ML, CO desorption becomes more favorable than dissociation. By applying the atomistic thermodynamics method, the determination of stable coverage as a function of temperature and partial pressure provides useful information, not only for surface science studies under ultrahigh vacuum conditions, but also for practical applications at high temperature and pressure in exploring reactions.