All-natural 2D nanofluidics as highly-efficient osmotic energy generators.

Two-dimensional nanofluidics based on naturally abundant clay are good candidates for harvesting osmotic energy between the sea and river from the perspective of commercialization and environmental sustainability. However, clay-based nanofluidics outputting long-term considerable osmotic power remains extremely challenging to achieve due to the lack of surface charge and mechanical strength. Here, a two-dimensional all-natural nanofluidic (2D-NNF) is developed as a robust and highly efficient osmotic energy generator based on an interlocking configuration of stacked montmorillonite nanosheets (from natural clay) and their intercalated cellulose nanofibers (from natural wood). The generated nano-confined interlamellar channels with abundant surface and space negative charges facilitate selective and fast hopping transport of cations in the 2D-NNF. This contributes to an osmotic power output of ~8.61 W m-2 by mixing artificial seawater and river water, higher than other reported state-of-the-art 2D nanofluidics. According to detailed life cycle assessments (LCA), the 2D-NNF demonstrates great advantages in resource consumption (1/14), greenhouse gas emissions (1/9), and production costs (1/13) compared with the mainstream 2D nanofluidics, promising good sustainability for large-scale and highly-efficient osmotic power generation.

Bio-Inspired Far-From-Equilibrium Hydrogels: Design Principles and Applications.

Inspired from dynamic living systems that operate under out-of-equilibrium conditions in biology, developing supramolecular hydrogels with self-regulating and autonomously dynamic properties to further advance adaptive hydrogels with life-like behavior is important. This review presents recent progress of bio-inspired supramolecular hydrogels out-of-equilibrium. The principle of out-of-equilibrium self-assembly for creating bio-inspired hydrogels is discussed. Various design strategies have been identified, such as chemical-driven reaction cycles with feedback control and physically oscillatory systems. These strategies can be coupled with hydrogels to achieve temporal and spatial control over structural and mechanical properties as well as programmable lifetime. These studies open up huge opportunities for potential applications, such as fluidic guidance, information storage, drug delivery, actuators and more. Finally, we address the challenges ahead of us in the coming years, and future possibilities and prospects are identified.

Regulation of Chiral Phosphoric Acid Catalyzed Asymmetric Reaction through Crown Ether Based Host-Guest Chemistry.

Supramolecular asymmetric catalysis has arisen from the in-depth intersection of supramolecular chemistry and asymmetric catalysis due to its unique advantages in building chiral catalyst libraries and regulating performance of catalysts. Herein, we combine crown ether based host-guest chemistry with chiral phosphoric acid mediated asymmetric catalysis to actualize the supramolecular regulation of catalytic asymmetric two-component tandem acetalization reactions. By comparison with the catalytic reaction without host-guest interaction, improvement of up to 72% in yield and increases of up to 13% in enantioselectivity were acquired after addition of the alkali metal guests, which demonstrated the great advantages of this supramolecular regulation strategy.

Switchable Polymerization Organocatalysis: From Monomer Mixtures to Block Copolymers.

One-pot production of sequence-controlled block copolymer from mixed monomers is a crucial but rarely reached goal. Using a switchable Lewis-pair organocatalyst, we have accomplished sequence-selective polymerization from a mixture of O-carboxyanhydride (OCA) and epoxide. Polymerization of the OCA monomer occurs first and exclusively because of its exceedingly high polymerizability. When OCA is fully consumed, alternating copolymerization of epoxide and CO2 liberated in OCA polymerization is triggered from the termini of the first block. The two polymerizations thus occur in tandem, both in chemoselective fashion, so that a sequence-controlled block polymer with up to 99 % CO2 conversion is furnished in this one-pot protocol. Calculations and experimental results demonstrate a chemoselective and cooperative mechanism, where the high polymerizability of the OCA monomers guarantees exquisite sequence selectivity and the cooperative decarboxylation partly arose from the stabilization effect by triethylborane, which facilitates the smooth transformation of the chain end from carbonate to alkoxide.

Crown Ether-Derived Chiral BINOL: Enantioselective Michael Addition of Alkenyl Boronic Acids to α,ß-Unsaturated Ketones.

A new class of aza-crown ether-derived chiral BINOL catalysts were designed, synthesized, and applied in the asymmetric Michael addition of alkenylboronic acids to α,ß-unsaturated ketones. It was found that introducing aza-crown ethers to the BINOL catalyst could achieve apparently higher enantioselectivity than a similar BINOL catalyst without aza-crown ethers did, although the host-guest complexation of alkali ions by the aza-crown ethers could not further improve the catalysis effectiveness. Under mediation of the aza-crown ether-derived chiral BINOL and in the presence of a magnesium salt, an array of chiral γ,δ-unsaturated ketones were furnished in good enantioselectivities (81-95% ees).

Two-dimensional materials towards separator functionalization in advanced Li-S batteries.

Functional separators have played important roles in improving the electrochemical performance of lithium-sulfur (Li-S) batteries by addressing the key issues of both the sulfur cathode and lithium anode. Compared with other materials that are used for separator functionalization, two-dimensional (2D) materials with atomic layer thickness and infinite lateral dimensions feature several advantages of ultra-thin laminate structure, remarkable physical properties and tunable surface chemistry, which show potential applications in separator functionalization towards addressing the issues of both the shuttle effect and formation of Li dendrites in Li-S batteries. In this review, the unique advantages of 2D materials for separator functionalization in Li-S batteries and their common construction methods are introduced. Then, recent progress and advances in the construction of 2D materials functional separators are summarized in detail towards inhibiting the shuttle effect of polysulfides and suppressing Li dendrite growth in Li-S batteries. Finally, some opportunities and challenges of 2D materials for constructing high-performance functional separators are proposed. We anticipate that this review will provide new insights into separator functionalization for developing advanced Li-S batteries.

Self-assembly of chiral BINOL cages via imine condensation.

Condensation of an (S)- or (R)-BINOL-derived dialdehyde and tris(2-aminoethyl)amine produced chiral [2+3] imine cages, which were further reduced to furnish more stable chiral amine cages and applied in the enantioselective recognition of (1R,2R)- and (1S,2S)-1,2-diaminocyclohexane.

Functional separators towards the suppression of lithium dendrites for rechargeable high-energy batteries.

Lithium metal battery (LMB) is considered to be one of the most promising electrochemical energy storage devices due to the high theoretical specific capacity and the lowest redox potential of metallic lithium; however, some key issues caused by lithium dendrites on the lithium metal anode seriously hinder its real-world applications. As an indispensable part of LMBs, the separator could serve as a physical barrier to prevent direct contact of the two electrodes and control ionic transport in batteries; it is an ideal platform for the suppression of lithium dendrites. In this review, the mechanism of lithium dendrite nucleation and growth are firstly discussed and then some advanced techniques are introduced for the precise characterization of lithium dendrites. On the basis of dendritic nucleation and growth principle, several feasible strategies are summarized for suppressing lithium dendrites by utilizing functional separators, including providing a mechanical barrier, promoting homogeneous lithium deposition, and regulating ionic transport. Finally, some challenges and prospects are proposed to clear the future development of functional separators. We anticipate that this paper will provide a new insight into the design and construction of functional separators for addressing the issues of lithium dendrites in high-energy batteries.

Cation-Selective Separators for Addressing the Lithium-Sulfur Battery Challenges.

Lithium-sulfur batteries (LSBs) have become one of the most promising candidates for next-generation energy storage systems owing to their high theoretical energy density, environmental friendliness, and cost effectiveness. However, real-word applications are seriously restricted by an undesirable shuttle effect and Li dendrite formation. In essence, uncontrollable anion transport is a key factor that causes both polysulfide shuttling and dendrite formation, which creates the possibility of simultaneously addressing the two critical issues in LSBs. An effective strategy to control anion transport is the construction of cation-selective separators. Significant progress has been achieved in the inhibition of the shuttle effect, whereas addressing the problem of Li dendrite formation by utilizing a cation-selective separator is still under way. From this viewpoint, this Review analyzes critical issues with regard to the shuttle effect and Li dendrite formation caused by uncontrollable anion transport, based on which roles and advantages of cation-selective separators toward high-performance LSBs are presented. According to the separator-construction principle, the latest advances and progress in cation-selective separators in inhibiting the shuttle effect and Li dendrite formation are reviewed in detail. Finally, some challenges and prospects are proposed for the future development of cation-selective separators. This Review is anticipated to provide a new perspective for simultaneously addressing the two critical issues in LSBs.

Chiral Metallacycles as Catalysts for Asymmetric Conjugate Addition of Styrylboronic Acids to α,ß-Enones.

Introducing self-assembly strategies into the construction of catalysts has been proven to have great advantages in asymmetric catalysis. We constructed two chiral metalla-triangles by highly efficient coordination-driven self-assembly from a chiral 3,3'-dipyridyl-substituted BINOL donor. They were successfully applied in asymmetric conjugate addition of a series of α,ß-unsaturated ketones with trans-styrylboronic acids. The use of these metalla-triangles as supramolecular catalysts is obviously conducive to the enhancement of catalytic activity and stereoselectivity in the presented addition reactions. Under induction of the chiral metalla-triangles, an array of α,ß-enones were converted to chiral γ,δ-unsaturated ketones in medium to quantitative yields (40-98%) with high enantioselectivities (87-96% ee).

Synergetic Organocatalysis for Eliminating Epimerization in Ring-Opening Polymerizations Enables Synthesis of Stereoregular Isotactic Polyester.

Ring-opening polymerization of O-carboxyanhydrides (OCAs) can furnish polyesters with a diversity of functional groups that are traditionally hard to harvest by polymerization of lactones. Typical ring-opening catalysts are subject to unavoidable racemization of most OCA monomers, which hampers the synthesis of highly isotactic crystalline polymers. Here, we describe an effective bifunctional single-molecule organocatalysis for selective ring-opening polymerization of OCAs without epimerization. The close vicinity of both activating groups in the same molecule engenders an amplified synergetic effect and thus allows for the use of mild bases, thereby leading to minimal epimerization for polymerization. Ring-opening polymerization of manOCA monomer (OCA from mandelic acid) mediated by the bifunctional single-molecule organocatalyst yields highly isotactic poly(mandelic acid) (PMA) with controlled molecular weights (up to 19.8 kg mol-1). Mixing of the two enantiomers of PMA generates the first example of a crystalline stereocomplex in this area, which displayed distinct Tm values around 150 °C. Remarkably, the bifunctional catalysts are moisture-stable, recyclable, and easy to use, allowing sustainable and scalable synthesis of a stereoregular functional polyester.