An Ultrasmall Ordered High-Entropy Intermetallic with Multiple Active Sites for the Oxygen Reduction Reaction.

Controlling multimetallic ensembles at the atomic level is significantly challenging, particularly for high-entropy alloys with more than five elements. Herein, we report an innovative ultrasmall (∼2 nm) PtFeCoNiCuZn high-entropy intermetallic (PFCNCZ-HEI) with a well-ordered structure synthesized by using the space-confined strategy. By exploiting these combined metals, the PFCNCZ-HEI nanoparticles achieve an ultrahigh mass activity of 2.403 A mgPt-1 at 0.90 V vs reversible hydrogen electrode for the oxygen reduction reaction, which is up to 19-fold higher than that of state-of-the-art commercial Pt/C. A proton exchange membrane fuel cell assembled with PFCNCZ-HEI as the cathode (0.03 mgPt cm-2) exhibits a power density of 1.4 W cm-2 and a high mass-normalized rated power of 45 W mgPt-1. Furthermore, theoretical calculations reveal that the outer electrons of the non-noble-metal atoms on the surface of the PFCNCZ-HEI nanoparticle are modulated to show characteristics of multiple active centers. This work offers a promising catalyst design direction for developing highly ordered HEI nanoparticles for electrocatalysis.

Three-Dimensional Covalent Organic Framework with ceq Topology.

Three-dimensional covalent organic frameworks (3D-COFs) are emerging as designable porous materials because of their unique structural characteristics and porous features. However, because of the lack of 3D organic building units and the less reversible covalent bonds, the topologies of 3D-COFs to date have been limited to dia, ctn, ffc, bor, rra, srs, pts, lon, stp, acs, tbo, bcu, and fjh. Here we report a 3D-COF with the ceq topology utilizing a D3h-symmetric triangular prism vertex with a planar triangular linker. The as-synthesized COF displays a twofold-interpenetrated structure with a Brunauer-Emmett-Teller surface area of 1148.6 m2 g-1. Gas sorption measurements revealed that 3D-ceq-COF could efficiently absorb CO2, CH4, and H2 under a moderate surface area. This work provides new building units and approaches for structural and application exploration of 3D-COFs.

An entanglement association polymer electrolyte for Li-metal batteries.

To improve the interface stability between Li-rich Mn-based oxide cathodes and electrolytes, it is necessary to develop new polymer electrolytes. Here, we report an entanglement association polymer electrolyte (PVFH-PVCA) based on a poly (vinylidene fluoride-co-hexafluoropropylene) (PVFH) matrix and a copolymer stabilizer (PVCA) prepared from acrylonitrile, maleic anhydride, and vinylene carbonate. The entangled structure of the PVFH-PVCA electrolyte imparts excellent mechanical properties and eliminates the stress arising from dendrite growth during cycling and forms a stable interface layer, enabling Li//Li symmetric cells to cycle steadily for more than 4500 h at 8 mA cm-2. The PVCA acts as a stabilizer to promote the formation of an electrochemically robust cathode-electrolyte interphase. It delivers a high specific capacity and excellent cycling stability with 84.7% capacity retention after 400 cycles. Li1.2Mn0.56Ni0.16Co0.08O2/PVFH-PVCA/Li full cell achieved 125 cycles at 1 C (4.8 V cut-off) with a stable discharge capacity of ~2.5 mAh cm-2.

Unlocking the Potential of Li-Rich Mn-Based Oxides for High-Rate Rechargeable Lithium-Ion Batteries.

Lithium-rich Mn-based oxides have gained significant attention worldwide as potential cathode materials for the next generation of high-energy density lithium-ion batteries. Nonetheless, the inferior rate capability and voltage decay issues present formidable challenges. Here, a Li-rich material equipped with quasi-three-dimensional (quasi-3D) Li-ion diffusion channels is initially synthesized by introducing twin structures with high Li-ion diffusion coefficients into the crystal and constructing a "bridge" between different Li-ion diffusion tunnels. The as-prepared material exhibits monodispersed micron-sized primary particles (MP), delivering a specific capacity of 303 mAh g-1 at 0.1 C and an impressive capacity of 253 mAh g-1 at 1 C. More importantly, the twin structure also serves as a "breakwater" to inhibit the migration of Mn ions and improve the overall structural stability, leading to cycling stability with 85% capacity retention at 1 C after 200 cycles. The proposed strategy of constructing quasi-3D channels in the layered Li-rich cathodes will open up new avenues for the research and development of other layered oxide cathodes, with potential applications in industry.

Entropy Stabilization Strategy for Enhancing the Local Structural Adaptability of Li-Rich Cathode Materials.

Layered Li-rich cathode materials with high reversible energy densities are becoming prevalent. However, owing to the activation of low-potential redox couples and the progressively irreversible structural transformation caused by the local adjustment of transition-metal ions in the intra/interlayer driven by anionic redox, continuous capacity degradation, and voltage decay emerge, thus greatly reducing the energy density and increasing the difficulty of battery system management. Herein, layered Li-rich cathode materials with higher intralayer configuration entropy have more local structural diversity and higher distortion energy, resulting in superior local structural adaptability with no drastic redox couple evolution, major local structural adjustment, or obvious layered-to-spinel phase transition. Consequently, the energy retention of the entropy-stabilization-strategy-enhanced Li-rich cathode materials is almost twice that of a typical Li-rich cathode material (Li1.20 Mn0.54 Ni0.13 Co0.13 O2 , T-LRM) after 3 months of cyclic testing. Moreover, when cycled at 1 C, the voltage degradation per cycle is less than 0.02%, that is, it results in a voltage loss of only 0.8 mV per cycle, which is excellent performance. This study paves the way for the development of Li-rich cathode materials with stabilized intralayer atomic arrangements and high local structural adaptability.

An asymmetric quasi-solid electrolyte for high-performance Li metal batteries.

We propose an asymmetric quasi-solid electrolyte to regulate Li deposition and avoid Li dendrite formation. The thiourea in the electrolyte can absorb on the Li surface to induce Li deposition, change the propagative growth behavior of Li metal and eliminate dendritic formation, thereby ensuring excellent cycling stability and high specific capacity.

Thiol-Branched Solid Polymer Electrolyte Featuring High Strength, Toughness, and Lithium Ionic Conductivity for Lithium-Metal Batteries.

Lithium-metal batteries (LMBs) with high energy densities are highly desirable for energy storage, but generally suffer from dendrite growth and side reactions in liquid electrolytes; thus the need for solid electrolytes with high mechanical strength, ionic conductivity, and compatible interface arises. Herein, a thiol-branched solid polymer electrolyte (SPE) is introduced featuring high Li+ conductivity (2.26 × 10-4 S cm-1 at room temperature) and good mechanical strength (9.4 MPa)/toughness (≈500%), thus unblocking the tradeoff between ionic conductivity and mechanical robustness in polymer electrolytes. The SPE (denoted as M-S-PEGDA) is fabricated by covalently cross-linking metal-organic frameworks (MOFs), tetrakis (3-mercaptopropionic acid) pentaerythritol (PETMP), and poly(ethylene glycol) diacrylate (PEGDA) via multiple CSC bonds. The SPE also exhibits a high electrochemical window (>5.4 V), low interfacial impedance (<550 Ω), and impressive Li+ transference number (tLi+ = 0.44). As a result, Li||Li symmetrical cells with the thiol-branched SPE displayed a high stability in a >1300 h cycling test. Moreover, a Li|M-S-PEGDA|LiFePO4 full cell demonstrates discharge capacity of 143.7 mAh g-1 and maintains 85.6% after 500 cycles at 0.5 C, displaying one of the most outstanding performances for SPEs to date.

5-aminolevulinic acid improves salt tolerance mediated by regulation of tetrapyrrole and proline metabolism in Brassica napus L. seedlings under NaCl stress.

5-aminolevulinic acid (ALA), a key biosynthetic precursor of tetrapyrroles, is vital for plant growth and adaptation to stress environments. Although exogenous ALA could enhance photosynthesis and biomass accumulation in plants under stress conditions, the underlying physiological and molecular mechanisms governed by ALA in promoting salt tolerance in Brassica napus L. are not yet clearly understood. In the present study, exogenous ALA with the concentration of 30 mg L-1 was applied to the leaves of B. napus seedlings subjected to 200 mM NaCl. The results showed that NaCl stress decreased the photosynthesis, biomass accumulation, and levels of chlorophyll and heme with the reduction of the concentrations of intermediates including ALA, protoporphyrin IX (Proto IX), Mg-Proto IX, and Pchlide in the tetrapyrrole (chlorophyll and heme) biosynthetic pathway. The transcript levels of genes encoding ALA-associated enzymes and genes encoding Mg-chelatase in the chlorophyll biosynthetic branch were down-regulated, while the expression levels of genes encoding Fe-chelatase in the heme branch were not significantly altered by NaCl stress. Foliar application with ALA enhanced the aboveground biomass, net photosynthetic rate, activities of antioxidant enzymes, accumulation of chlorophyll and heme, and concentrations of intermediates related to chlorophyll and heme biosynthesis in B. napus under 200 mM NaCl. The expression of most genes mentioned above remained constant in ALA-treated plants in comparison with non-ALA-treated plants under NaCl stress. Additionally, exogenous ALA synchronously induced the proline concentration and up-regulated the expression of genes P5CS and ProDH encoding proline metabolic enzymes in the NaCl treatment. These findings suggested that ALA improved salt tolerance through promoting the accumulation of chlorophyll and heme resulting from the increase of intermediate levels in the tetrapyrrole biosynthetic pathway, along with enhancing the proline accumulation in B. napus.

Fullerol improves seed germination, biomass accumulation, photosynthesis and antioxidant system in Brassica napus L. under water stress.

Carbon nanoparticles are widely studied for affecting crop production in agriculture. Considering their potential threats to the crops, especially under drought stress, is important for carbon nanoparticle application. However, the influence of polyhydroxy fullerene-fullerol on drought tolerance at the physiological and molecular levels in Brassica napus remains unclear. In the present study, different doses of fullerol were applied to seeds or leaves of B. napus subjected to water stress. The results showed that water stress significantly reduced the seed germination, aboveground dry weight, and photosynthesis, whereas it increased the abscisic acid (ABA) concentration, reactive oxygen species (ROS) accumulation, levels of non-enzymatic substances, and activities of antioxidant enzymes in B. napus. Priming with fullerol at 10 and 100 mg L-1 in seeds exhibited a significant promotional effect on seed germination under 15% polyethylene glycol treatment. Moreover, foliar application of fullerol raised the aboveground dry weight and photosynthesis in B. napus seedlings under soil drying. Compared with soil drying alone, the accumulation of ROS was repressed, which was concomitant with higher concentrations of non-antioxidant substances and increased activities of antioxidant enzymes in leaves of seedlings exposed to fullerol at specific concentrations addition with water shortage. Fullerol treatments at 1-100 mg L-1 dramatically increased the leaf ABA level and induced ABA biosynthesis by down-regulating the expression of the ABA catabolic gene CYP707A3 under drought. It is concluded that exogenous fullerol with seed priming or foliar application can stimulate growth in B. napus when water-stressed. The increased antioxidant ability that collectively detoxified ROS improved the drought tolerance in B. napus seedlings under foliar-applied fullerol treatment.