Formic acid (HCOOH) is one of the most promising chemical fuels that can be produced through CO2 electroreduction. However, most of the catalysts for CO2 electroreduction to HCOOH in aqueous solution ...often suffer from low current density and limited production rate. Herein, we provide a bismuth/cerium oxide (Bi/CeOx) catalyst, which exhibits not only high current density (149 mA cm−2), but also unprecedented production rate (2600 μmol h−1 cm−2) with high Faradaic efficiency (FE, 92 %) for HCOOH generation in aqueous media. Furthermore, Bi/CeOx also shows favorable stability over 34 h. We hope this work could offer an attractive and promising strategy to develop efficient catalysts for CO2 electroreduction with superior activity and desirable stability.
The limited current density, production rate as well as selectivity hinder the improvement of HCOOH production from CO2 electroreduction. Here, bismuth/cerium oxide (Bi/CeOx) displays outstanding performances for CO2 electroreduction to HCOOH, which not only shows excellent selectivity, but also achieves a high current density (149 mA cm−2) and especially the maximum HCOOH production rate (2600 μmol h−1 cm−2) ever reported.
To achieve high performed zinc metal batteries, it is imperative to address the issues of dendrite growth and the side‐reactions occurring at the Zn anode, particularly when the batteries are ...operated at high current densities and high temperature. Herein, a flexible and dendrite‐free Zn metal anode (AgNPs@CC/Zn), which is prepared by inkjet printing silver nanoparticles on a 3D carbon matrix, is reported. Experimental observations and DFT calculation reveal that the Ag nanoparticles can work as heterometallic seeds for zinc deposition, and thus simultaneously improve the zincophilicity and thermal conductivity of the carbon matrix. This not only lowers the Zn nucleation overpotential and guides the uniform Zn nucleation but also promotes the reversible zinc stripping/plating via AgZn alloying/de‐alloying reactions. As a result, the AgNPs@CC/Zn anode presents low voltage hysteresis of 80 mV and superior cycling over 480 h at a high current density of 10 mA cm−2. The AgNPs@CC/Zn anode can enable full cells with exceptional cyclic stability and enhanced high‐temperature endurance. Furthermore, the foldable pouch cell using the AgNPs@CC/Zn anode exhibits high capacity retention regardless of different deformation status. This work demonstrates the promising potential of inkjet printing technology in developing 3D dendrite‐free zinc anode for foldable and heat‐resistant zinc batteries.
A flexible and dendrite‐free Zn metal anode is prepared by inkjet printing silver nanoparticles on a 3D carbon matrix, boosting electrochemical performance of zinc metal batteries. The Ag nanoparticles as heterometallic seeds can promote reversible zinc stripping/plating via AgZn alloying/de‐alloying reactions and improve the zincophilicity and thermal conductivity of the carbon matrix.
Efficient and selective dehydrogenation of formic acid is a key challenge for a fuel‐cell‐based hydrogen economy. Though the development of heterogeneous catalysts has received much progress, their ...catalytic activity remains insufficient. Moreover, the design principle of such catalysts are still unclear. Here, experimental and theoretical studies on a series of mono‐/bi‐metallic nanoparticles supported on a NH2‐N‐rGO substrate are combined for formic acid dehydrogenation where the surface energy of a metal is taken as a relevant indicator for the adsorption ability of the catalyst for guiding catalyst design. The AuPd/NH2‐N‐rGO catalyst shows record catalytic activity by reducing the energy barrier of rate controlling steps of formate adsorption and hydrogen desorption. The obtained excellent results both in experiments and simulations could be extended to other important systems, providing a general guideline to design more efficient catalysts.
A AuPd/NH2‐N‐rGO catalyst shows supreme catalytic performance for the decomposition of formic acid at room temperature, with a turnover frequency (TOF) of 4445.6 h−1. Developments in the experiments and simulations of high‐performance catalysts may promote the practical application of formic acid as a promising hydrogen storage material.
Conversion of air and water into valuable chemicals of ammonia (NH3) by plasma activation and electrochemical reduction is a promising approach to achieve zero carbon‐emission synthesis of NH3. ...However, designing highly efficient electrochemical catalysts is one of the key challenges in accomplishing this strategy. Herein, a self‐supported cobalt–tungsten alloy supported on cobalt foam (CoW/CF) is developed via a simple and efficient method at room temperature. Surprisingly, the catalyst exhibits ultra‐high NH3 partial current density (1559 mA cm−2), superior NH3 yield rate (164.3 mg h−1 cm−2), and high Faradaic efficiency (98.1%) under the condition of 0.2 M nitrate/nitrite, outperforming most of the reported values of electrosynthesis of NH3 to the knowledge. The introduction of W makes the Co atom surface electron deficient, which can enhance the adsorption of NOx− and mitigate the excessive bonding of hydroxyl radicals (OH*) generated during nitrite (NO2*) hydrogenation, thereby reducing the energy barrier of the potential‐determining step. More interestingly, a scale‐up reaction system is established, achieving an NH3 yield rate of 4.771 g h−1 and successfully converting the NH3 in solution into solid NH4Cl. The aforementioned progress significantly enhances the facilitation of NH3 electrosynthesis industrialization.
A self‐supported CoW/CF catalyst is developed to efficiently synthesize NH3. Through the combination of plasma and electrocatalysis, the catalyst shows an impressive NH3 yield rate of 164.3 mg h−1 cm−2 and an excellent FE of 98.2%. Additionally, a gram‐level NH3 yield rate of 4.771 g h−1 can be achieved and effectively converted into a multifunctional solid of NH4Cl.
Ambient electrochemical ammonia (NH3) synthesis is one promising alternative to the energy‐intensive Haber–Bosch route. However, the industrial requirement for the electrochemical NH3 production with ...amperes current densities or gram‐level NH3 yield remains a grand challenge. Herein, we report the high‐rate NH3 production via NO2− reduction using the Cu activated Co electrode in a bipolar membrane (BPM) assemble electrolyser, wherein BPM maintains the ion balance and the liquid level of electrolyte. Benefited from the abundant Co sites and optimal structure, the target modified Co foam electrode delivers a current density of 2.64 A cm−2 with the Faradaic efficiency of 96.45 % and the high NH3 yield rate of 279.44 mg h−1 cm−2 in H‐type cell using alkaline electrolyte. Combined with in situ experiments and theoretical calculations, we found that Cu optimizes the adsorption behavior of NO2− and facilitates the hydrogenation steps on Co sites toward a rapid NO2− reduction process. Importantly, this activated Co electrode affords a large NH3 production up to 4.11 g h−1 in a homemade reactor, highlighting its large‐scale practical feasibility.
A high‐efficiency electrochemical ammonia (NH3) synthesis from NOx on a Cu‐activated Co foam electrode was developed as a promising alternative for the Haber–Bosch process. The new synthesis can convert pollutants into elevated value‐added NH3 applicable for agriculture, energy storage, etc., imposing a sustainable nitrogen cycle.
Ammonia (NH3) is essential for modern agriculture and industry, and, due to its high hydrogen density and no carbon emission, it is also expected to be the next‐generation of “clean” energy carrier. ...Herein, directly from air and water, a plasma‐electrocatalytic reaction system for NH3 production, which combines two steps of plasma‐air‐to‐NOx− and electrochemical NOx− reduction reaction (eNOxRR) with a bifunctional catalyst, is successfully established. Especially, the bifunctional catalyst of CuCo2O4/Ni can simultaneously promote plasma‐air‐to‐NOx− and eNOxRR processes. The easy adsorption and activation of O2 by CuCo2O4/Ni greatly improve the NOx− production rate at the first step. Further, CuCo2O4/Ni can also resolve the overbonding of the key intermediate of *NO, and thus reduce the energy barrier of the second step of eNOxRR. Finally, the “green” NH3 production achieves excellent FENH3 (96.8%) and record‐high NH3 yield rate of 145.8 mg h−1 cm−2 with large partial current density (1384.7 mA cm−2). Moreover, an enlarged self‐made H‐type electrolyzer improves the NH3 yield to 3.6 g h−1, and the obtained NH3 is then rapidly converted to a solid of magnesium ammonium phosphate hexahydrate, which favors the easy storage and transportation of NH3.
A bifunctional catalyst of CuCo2O4/Ni applying to plasma‐electrocatalytic synthesis of NH3 from air and water is proposed, with which a record‐high NH3 yield rate of 145.8 mg h−1 cm−2 and excellent FE of 96.8% can be obtained. Moreover, the reaction system is enlarged and the generated NH3 precipitates into MgNH4PO4·6H2O solid to promote the practical application.
Acyl‑CoA synthetase long‑chain family member 4 (ACSL4) is a member of the long chain family of acyl‑CoA synthetase proteins, which have recently been shown to serve an important role in ferroptosis. ...Previous studies have suggested that ferroptosis is involved in the occurrence of glioma; however, the role of ACSL4 in glioma remains unknown. In the present study, a reduction of ferroptosis in human glioma tissues and glioma cells was observed. Subsequently, it was demonstrated that the expression of ACSL4 was also downregulated in human glioma tissues and cells. A ferroptosis inhibitor and inducer were used to investigate the effects of ferroptosis on viability. The results showed that promoting ferroptosis inhibited the proliferation of glioma cells, and that the use of inducers had the reverse effect. Therefore, it was hypothesized that the reduction in ACSL4 expression may have been involved in ferroptosis and proliferation in glioma. Overexpression of ACSL4 decreased expression of glutathione peroxidase 4 and increased the levels of ferroptotic markers, including 5‑hydroxyeicosatetraenoic (HETE), 12‑HETE and 15‑HETE. Additionally, ACSL4 overexpression resulted in an increase in lactate dehydrogenase release and a reduction in cell viability. The opposite results were observed when ACSL4 was silenced. These findings suggest that ACSL4 regulates ferroptosis and proliferation of glioma cells. To further investigate the mechanism underlying ACSL4‑mediated regulation of proliferation in glioma cells, cells were treated with small interfering (si)‑ACSL4 and sorafenib, a ferroptosis inducer. sorafenib attenuated the ability of siRNA‑mediated silencing of ACSL4, thus improving cell viability. These results demonstrate that ACSL4 protects glioma cells and exerts anti‑proliferative effects by activating a ferroptosis pathway and highlight the pivotal role of ferroptosis regulation by ACSL4 in its protective effects on glioma. Therefore, ACSL4 may serve as a novel therapeutic target for the treatment of glioma.
TDP-43 is a nuclear factor that functions in promoting pre-mRNA splicing. Deletion of the N-terminal domain (NTD) and nuclear localization signal (NLS) (i.e., TDP-35) results in mislocalization to ...cytoplasm and formation of inclusions. However, how the NTD functions in TDP-43 activity and proteinopathy remains largely unknown. Here, we studied the structure and function of the NTD in inclusion formation and pre-mRNA splicing of TDP-43 by using biochemical and biophysical approaches. We found that TDP-43 NTD forms a homodimer in solution in a concentration-dependent manner, and formation of intermolecular disulfide results in further tetramerization. Based on the NMR structure of TDP-43 NTD, the dimerization interface centered on Leu71 and Val72 around the β7-strand was defined by mutagenesis and size-exclusion chromatography. Cell experiments revealed that the N-terminal dimerization plays roles in protecting TDP-43 against formation of cytoplasmic inclusions and enhancing pre-mRNA splicing activity of TDP-43 in nucleus. This study may provide mechanistic insights into the physiological function of TDP-43 and its related proteinopathies.
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•Microstructure is analysed on different planes of SLM 316L stainless steel.•Scanning strategy and building direction affects microstructural characteristics.•Sample fabricated with ...67.5°-rotation scanning shows the lowest corrosion resistance.•The corrosion resistance of the planes perpendicular to building direction is higher.•The boundary of the molten pool is more susceptible to corrosion.
In-depth understanding of corrosion behaviour is a key aspect regarding the application of additively manufactured parts. In this study, 316L stainless steel was manufactured under different scanning strategies using selective laser melting (SLM). Microstructure characterization and electrochemical tests in NaCl aqueous solution (3.5 wt%), including open circuit potential (OCP), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS), were conducted to study the influence of scanning strategies on the corrosion behaviour. The microstructure and corrosion on different planes were characterized to reveal the influence of building direction. EBSD analysis shows that the scanning strategy affects the continuity of grain growth through adjacent layers and the growth of grains inside the melt track. Electrochemical tests indicate a clear difference in corrosion resistance perpendicular and parallel to building direction and with different scanning strategies. Pitting corrosion is the main form of corrosion in SLM 316L stainless steel and preferentially initiates on molten pool boundaries.
Heterotrimeric G proteins function as key players in hydrogen peroxide (H₂O₂) production in plant cells, but whether G proteins mediate ethylene‐induced H₂O₂production and stomatal closure are not ...clear. Here, evidences are provided to show the Gα subunit GPA1 as a missing link between ethylene and H₂O₂in guard cell ethylene signalling. In wild‐type leaves, ethylene‐triggered H₂O₂synthesis and stomatal closure were dependent on activation of Gα. GPA1 mutants showed the defect of ethylene‐induced H₂O₂production and stomatal closure, whereas wGα and cGα overexpression lines showed faster stomatal closure and H₂O₂production in response to ethylene. Ethylene‐triggered H₂O₂generation and stomatal closure were impaired in RAN1, ETR1, ERS1 and EIN4 mutants but not impaired in ETR2 and ERS2 mutants. Gα activator and H₂O₂rescued the defect of RAN1 and EIN4 mutants or etr1‐3 in ethylene‐induced H₂O₂production and stomatal closure, but only rescued the defect of ERS1 mutants or etr1‐1 and etr1‐9 in ethylene‐induced H₂O₂production. Stomata of CTR1 mutants showed constitutive H₂O₂production and stomatal closure, but which could be abolished by Gα inhibitor. Stomata of EIN2, EIN3 and ARR2 mutants did not close in responses to ethylene, Gα activator or H₂O₂, but do generate H₂O₂following challenge of ethylene or Gα activator. The data indicate that Gα mediates ethylene‐induced stomatal closure via H₂O₂production, and acts downstream of RAN1, ETR1, ERS1, EIN4 and CTR1 and upstream of EIN2, EIN3 and ARR2. The data also show that ETR1 and ERS1 mediate both ethylene and H₂O₂signalling in guard cells.
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