Designing atomically dispersed metal catalysts for oxygen reduction reaction (ORR) is a promising approach to achieve efficient energy conversion. Herein, we develop a template-assisted method to ...synthesize a series of single metal atoms anchored on porous N,S-codoped carbon (NSC) matrix as highly efficient ORR catalysts to investigate the correlation between the structure and their catalytic performance. The structure analysis indicates that an identical synthesis method results in distinguished structural differences between Fe-centered single-atom catalyst (Fe-SAs/NSC) and Co-centered/Ni-centered single-atom catalysts (Co-SAs/NSC and Ni-SAs/NSC) because of the different trends of each metal ion in forming a complex with the N,S-containing precursor during the initial synthesis process. The Fe-SAs/NSC mainly consists of a well-dispersed FeN4S2 center site where S atoms form bonds with the N atoms. The S atoms in Co-SAs/NSC and Ni-SAs/NSC, on the other hand, form metal–S bonds, resulting in CoN3S1 and NiN3S1 center sites. Density functional theory (DFT) reveals that the FeN4S2 center site is more active than the CoN3S1 and NiN3S1 sites, due to the higher charge density, lower energy barriers of the intermediates, and products involved. The experimental results indicate that all three single-atom catalysts could contribute high ORR electrochemical performances, while Fe-SAs/NSC exhibits the highest of all, which is even better than commercial Pt/C. Furthermore, Fe-SAs/NSC also displays high methanol tolerance as compared to commercial Pt/C and high stability up to 5000 cycles. This work provides insights into the rational design of the definitive structure of single-atom catalysts with tunable electrocatalytic activities for efficient energy conversion.
Sodium‐ion batteries capable of operating at rate and temperature extremes are highly desirable, but elusive due to the dynamics and thermodynamics limitations. Herein, a strategy of ...electrode–electrolyte interfacial chemistry modulation is proposed. The commercial hard carbon demonstrates superior rate performance with 212 mAh g−1 at an ultra‐high current density of 5 A g−1 in the electrolyte with weak ion solvation/desolvation, which is much higher than those in common electrolytes (nearly no capacity in carbonate‐based electrolytes). Even at −20 °C, a high capacity of 175 mAh g−1 (74 % of its room‐temperature capacity) can be maintained at 2 A g−1. Such an electrode retains 90 % of its initial capacity after 1000 cycles. As proven, weak ion solvation/desolvation of tetrahydrofuran greatly facilitates fast‐ion diffusion at the SEI/electrolyte interface and homogeneous SEI with well‐distributed NaF and organic components ensures fast Na+ diffusion through the SEI layer and a stable interface.
In a THF‐based electrolyte with a weak solvation structure, Na+ desolvation is fast and a uniform solid electrolyte interphase (SEI) with abundant NaF and organic compounds is generated on the commercial hard carbon anode. This greatly enhances the interface stability and enables the rapid migration of Na+ in the SEI, thus realizing the high rate capability, long‐term stability and good low‐temperature performance for the hard carbon anode.
Lithium-oxygen batteries (LOBs) promise high energy density but suffer from catalyst-related issues. We've developed FeNi-NCNT/DrGO, a novel catalyst, by integrating iron-nickel nanoalloys (FeNi) ...embedded in nitrogen-doped carbon nanotubes (NCNTs) grafted onto defect-rich reduced graphene oxide (DrGO). The fabrication involved freeze-drying, defect engineering, and thermal treatments. The FeNi nanoalloy within the catalyst demonstrates outstanding bifunctional activity, while the NCNTs serve as an excellent electronic conduction medium and DrGO enables favorable ion transport. The 3D open-space architecture of this catalyst provides a rapid diffusion path for the electrolyte and room for accommodating discharge products. As a result, the LOBs with FeNi-NCNT/DrGO exhibits exceptional electrochemical performance, achieving a deep discharge capacity of 21,153.6 mAh g−1 and a high round-trip efficiency of 98.7% at 200 mA g−1. Moreover, it demonstrates excellent cycling stability, exceeding 100 cycles at 200 mA g−1 with a cut-off capacity of 500 mAh g−1.
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•FeNi-NCNT/DrGO was formed by freeze-drying, ball milling, and thermal treatment.•The catalyst shows superior ORR, OER, conductivity, ion diffusion and Li2O2 storage.•LOB with the catalyst shows a capacity of 21153 mAhg−1 and 98.74% efficiency.•LOB exceeds 100 cycles at 200 mA g−1 with a cut-off capacity of 500 mAh g−1.
The ability to determine the electronic structure of catalysts during electrochemical reactions is highly important for identification of the active sites and the reaction mechanism. Here we ...successfully applied soft X-ray spectroscopy to follow in operando the valence and spin state of the Co ions in Li
Co
O
under oxygen evolution reaction (OER) conditions. We have observed that a substantial fraction of the Co ions undergo a voltage-dependent and time-dependent valence state transition from Co
to Co
accompanied by spontaneous delithiation, whereas the edge-shared Co-O network and spin state of the Co ions remain unchanged. Density functional theory calculations indicate that the highly oxidized Co
site, rather than the Co
site or the oxygen vacancy site, is mainly responsible for the high OER activity.
Anode‐free lithium‐metal batteries employ in situ lithium‐plated current collectors as negative electrodes to afford optimal mass and volumetric energy densities. The main challenges to such ...batteries include their poor cycling stability and the safety issues of the flammable organic electrolytes. Here, a high‐voltage 4.7 V anode‐free lithium‐metal battery is reported, which uses a Cu foil coated with a layer (≈950 nm) of silicon–polyacrylonitrile (Si‐PAN, 25.5 µg cm−2) as the negative electrode, a high‐voltage cobalt‐free LiNi0.5Mn1.5O4 (LNMO) as the positive electrode and a safe, nonflammable ionic liquid electrolyte composed of 4.5 m lithium bis(fluorosulfonyl)imide (LiFSI) salt in N‐methyl‐N‐propyl pyrrolidiniumbis(fluorosulfonyl)imide (Py13FSI) with 1 wt% lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as additive. The Si‐PAN coating is found to seed the growth of lithium during charging, and reversibly expand/shrink during lithium plating/stripping over battery cycling. The wide‐voltage‐window electrolyte containing a high concentration of FSI− and TFSI− facilitates the formation of stable solid‐electrolyte interphase, affording a 4.7 V anode‐free Cu@Si‐PAN/LiNi0.5Mn1.5O4 battery with a reversible specific capacity of ≈120 mAh g−1 and high cycling stability (80% capacity retention after 120 cycles). These results represent the first anode‐free Li battery with a high 4.7 V discharge voltage and high safety.
4.7 V Cu@Si‐PAN/LiNi0.5Mn1.5O4 anode‐free Li batteries with a reversible specific capacity of ≈120 mAh g−1 and high capacity retention of 80% after 120 cycles are reported. With the nonflammable F‐rich ionic liquid electrolyte and the seeding Si‐PAN layer (950 nm), an enhanced safety and high‐voltage anode‐free Li battery without dendritic Li growth is demonstrated.
Most existing deep learning (DL)-based health prognostic methods assume that the training and testing datasets are from identical machines operating under similar conditions requiring massive ...labelled condition monitoring (CM) data to guarantee the prediction accuracy and generalisation capacity. However, these strict restrictions significantly hinder the deployment of the dl-based prognostic methods in real industries. In this paper, a Bayesian semi-supervised transfer learning with active querying-based intelligent fault prognostic framework is developed for remaining useful life (RUL) prediction across completely different machines under limited data. The proposed method strategically integrates the advantages of transfer learning (TL) and active learning in the Bayesian deep learning (BDL) framework. In the proposed framework, Bayesian neural networks with Monte Carlo dropout inference are utilised to quantify RUL prediction uncertainty, which is further leveraged to develop an active querying-based training data selection mechanism. Moreover, TL is simultaneously embedded into the BDL framework to relieve data distribution discrepancies existing among the completely different machines. The experimental verifications from open-sourced bearing datasets and lab testing-based lithium-ion battery degradation datasets demonstrate that the proposed framework can effectively and reliably achieve bi-directional transfer fault prognostic tasks under limited labelled CM data in target domain. Finally, generalisation and superiority of the proposed method are also validated by comparing with other state-of-the-art methods.
Recycling of molybdenum isotopes in continental subduction zones remains debated. In this contribution, we re‐visit the Mo isotope compositions of the Sailipu post‐collisional ultrapotassic rocks in ...the Himalaya‐southern Tibet orogen. These ultrapotassic rocks have very varying δ98/95Mo values of −0.66 to −0.07‰ and Mo/Ce ratios of 0.0008–0.005, which are lower than those of mid‐ocean ridge basalts (MORB; δ98/95Mo = −0.20 ± 0.06‰, and Mo/Ce = 0.03) and oceanic subduction‐related (i.e., mantle source involving fluids, residual slab, or oceanic sediments) magmatic rocks (e.g., modern arc lavas, Cenozoic OIB‐type basalts in eastern China and the central Mariana Trough basalts in the back‐arc basin, syn‐collisional andesitic rocks in southern Tibet). Combined with the light Mo isotopes of the Himalayan schists and gneisses, we suggest that the light Mo isotopic signature of the Sailipu ultrapotassic rocks is derived from subducted Indian continental crust. This is consistent with the extremely low δ11B (−17.4 to −9.7‰) and B/Nb (0.16–1) values and enriched Sr‐Nd‐Pb isotopes of the Sailipu ultrapotassic rocks. Thus, this study reveals the recycling of light Mo‐B isotopes during continental subduction and demonstrates that Mo‐B isotopes can effectively distinguish between continental and oceanic subduction.
Plain Language Summary
Mo isotope systematics have been widely applied in the study of tracing recycled crustal materials, and abundant researches have proposed that heavy Mo isotopic compositions of arc‐mafic magma can be ascribed to slab‐dehydrated fluids. However, in continental subduction zones, the origin of the light Mo isotopes of post‐collisional mafic rocks (oceanic sediments during prior oceanic subduction vs. subducted continental crust) remains controversial, hindering our understanding of the recycling of continental crustal materials. In this study, we report new Mo isotope data of post‐collisional ultrapotassic rocks in the Lhasa block of the southern Tibetan plateau. We have used Mo isotope data along with B‐Sr‐Nd‐Pb isotopes of these ultrapotassic rocks, in combination with Mo‐B‐Sr‐Nd‐Pb isotopes of the Himalayan crustal rocks (e.g., gneisses and schists) to trace the crustal components in the post‐collisional mantle beneath southern Tibet. We concluded that the light Mo and B isotope compositions in southern Tibet were derived from subducted Indian continental crust rather than Neo‐Tethyan oceanic sediments. Thus, this study not only reveals the recycling of light Mo‐B isotopes in this typical collision orogen (i.e., Himalaya‐Tibet orogen) but also shows the potential in discriminating between oceanic subduction metasomatism and continental subduction metasomatism.
Key Points
Post‐collisional ultrapotassic rocks in southern Tibet have extremely light Mo and B isotope compositions
These light Mo‐B isotope features are derived from subducted Indian continental crust
Mo‐B isotopes have the potential to discriminate between oceanic and continental subduction
Itch and pain are refractory symptoms of many ocular conditions. Ocular itch is generated mainly in the conjunctiva and is absent from the cornea. In contrast, most ocular pain arises from the ...cornea. However, the underlying mechanisms remain unknown. Using genetic axonal tracing approaches, we discover distinct sensory innervation patterns between the conjunctiva and cornea. Further genetic and functional analyses in rodent models show that a subset of conjunctival-selective sensory fibers marked by MrgprA3 expression, rather than corneal sensory fibers, mediates ocular itch. Importantly, the actions of both histamine and nonhistamine pruritogens converge onto this unique subset of conjunctiva sensory fibers and enable them to play a key role in mediating itch associated with allergic conjunctivitis. This is distinct from skin itch, in which discrete populations of sensory neurons cooperate to carry itch. Finally, we provide proof of concept that selective silencing of conjunctiva itch-sensing fibers by pruritogen-mediated entry of sodium channel blocker QX-314 is a feasible therapeutic strategy to treat ocular itch in mice. Itch-sensing fibers also innervate the human conjunctiva and allow pharmacological silencing using QX-314. Our results cast new light on the neural mechanisms of ocular itch and open a new avenue for developing therapeutic strategies.
Producing indispensable hydrogen and oxygen for social development via water electrolysis shows more prospects than other technologies. Although electrocatalysts have been explored for centuries, a ...universal activity descriptor for both hydrogen‐evolution reaction (HER) and oxygen‐evolution reaction (OER) is not yet developed. Moreover, a unifying concept is not yet established to simultaneously understand HER/OER mechanisms. Here, the relationships between HER/OER activities in three common electrolytes and over ten representative material properties on 12 3d‐metal‐based model oxides are rationally bridged through statistical methodologies. The orbital charge‐transfer energy (Δ) can serve as an ideal universal descriptor, where a neither too large nor too small Δ (≈1 eV) with optimal electron‐cloud density around Fermi level affords the best activities, fulfilling Sabatier's principle. Systematic experiments and computations unravel that pristine oxide with Δ ≈ 1 eV possesses metal‐like high‐valence configurations and active lattice‐oxygen sites to help adsorb key protons in HER and induce lattice‐oxygen participation in the OER, respectively. After reactions, partially generated metals in the HER and high‐valence hydroxides in the OER dominate proton adsorption and couple with pristine lattice‐oxygen activation, respectively. These can be successfully rationalized by the unifying orbital charge‐transfer theory. This work provides the foundation of rational material design and mechanism understanding for many potential applications.
A universal activity descriptor (orbital charge‐transfer energy) is successfully extracted from various materials’ physicochemical properties for both hydrogen‐evolving and oxygen‐evolving reactions in multiple electrolytes. Systematic experiments and computations reveal the life‐cycle HER and OER mechanisms and identify the unifying orbital charge‐transfer theory as a powerful mechanism analysis tool and foundation.
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