Surface atom knockout for the active site exposure of alloy catalyst.

The fine regulation of catalysts by the atomic-level removal of inactive atoms can promote the active site exposure for performance enhancement, whereas suffering from the difficulty in controllably removing atoms using current micro/nano-scale material fabrication technologies. Here, we developed a surface atom knockout method to promote the active site exposure in an alloy catalyst. Taking Cu3Pd alloy as an example, it refers to assemble a battery using Cu3Pd and Zn as cathode and anode, the charge process of which proceeds at about 1.1 V, equal to the theoretical potential difference between Cu2+/Cu and Zn2+/Zn, suggesting the electricity-driven dissolution of Cu atoms. The precise knockout of Cu atoms is confirmed by the linear relationship between the amount of the removed Cu atoms and the battery cumulative specific capacity, which is attributed to the inherent atom-electron-capacity correspondence. We observed the surface atom knockout process at different stages and studied the evolution of the chemical environment. The alloy catalyst achieves a higher current density for oxygen reduction reaction compared to the original alloy and Pt/C. This work provides an atomic fabrication method for material synthesis and regulation toward the wide applications in catalysis, energy, and others.

Microfluidic-Assisted Self-Assembly of Molecular Hydrogelator at Water-Water Interfaces for Continuous Fabrication of Supramolecular Microcapsules.

Control over the self-assembly of small molecules at specific areas is of great interest for many high-tech applications, yet remains a formidable challenge. Here, how the self-assembly of hydrazone-based molecular hydrogelators can be specifically triggered at water-water interfaces for the continuous fabrication of supramolecular microcapsules by virtue of the microfluidic technique is demonstrated. The non-assembling hydrazide- and aldehyde-based hydrogelator precursors are distributed in two immiscible aqueous polymer solutions, respectively, through spontaneous phase separation. In the presence of catalysts, hydrazone-based hydrogelators rapidly form and self-assemble into hydrogel networks at the generated water-water interfaces. Relying on the microfluidic technique, microcapsules bearing a shell of supramolecular hydrogel are continuously produced. The obtained microcapsules can effectively load enzymes, enabling localized enzymatic growth of supramolecular fibrous supramolecular structures, reminiscent of the self-assembly of biological filaments within living cells. This work may contribute to the development of biomimetic supramolecular carriers for applications in biomedicine and fundamental research, for instance, the construction of protocells.

Plasma-Driven Efficient Conversion of CO2 and H2O into Pure Syngas with Controllable Wide H2/CO Ratios over Metal-Organic Frameworks Featuring In Situ Evolved Ligand Defects.

While the mild production of syngas (a mixture of H2 and CO) from CO2 and H2O is a promising alternative to the coal-based chemical engineering technologies, the inert nature of CO2 molecules, unfavorable splitting pathways of H2O and unsatisfactory catalysts lead to the challenge in the difficult integration of high CO2 conversion efficiency with produced syngas with controllable H2/CO ratios in a wide range. Herein, we report an efficient plasma-driven catalytic system for mild production of pure syngas over porous metal-organic framework (MOF) catalysts with rich confined H2O molecules, where their syngas production capacity is regulated by the in situ evolved ligand defects and the plasma-activated intermediate species of CO2 molecules. Specially, the Cu-based catalyst system achieves 61.9 % of CO2 conversion and the production of pure syngas with wide H2/CO ratios of 0.05 : 1-4.3 : 1. As revealed by the experimental and theoretical calculation results, the in situ dynamic structure evolution of Cu-containing MOF catalysts favors the generation of coordinatively unsaturated metal active sites with optimized geometric and electronic characteristics, the adsorption of reactants, and the reduced energy barriers of syngas-production potential-determining steps of the hydrogenation of CO2 to *COOH and the protonation of H2O to *H.

Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron-based Metal-Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis.

Engineering advantageous defects to construct well-defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe-based metal-organic framework (MOF) photocatalysts via a non-thermal plasma-assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH- and H2O). Specially, the optimized MIL-100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7- and 7.7-fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d-orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high-performance activation of catalytic molecules.

Spatiotemporal control over self-assembly of supramolecular hydrogels through reaction-diffusion.

Supramolecular self-assembly is ubiquitous in living system and is usually controlled to proceed in time and space through sophisticated reaction-diffusion processes, underpinning various vital cellular functions. In this contribution, we demonstrate how spatiotemporal self-assembly of supramolecular hydrogels can be realized through a simple reaction-diffusion-mediated transient transduction of pH signal. In the reaction-diffusion system, a relatively faster diffusion of acid followed by delayed enzymatic production and diffusion of base from the opposite site enables a transient transduction of pH signal in the substrate. By coupling such reaction-diffusion system with pH-sensitive gelators, dynamic supramolecular hydrogels with tunable lifetimes are formed at defined locations. The hydrogel fibers show interesting dynamic growing behaviors under the regulation of transient pH signal, reminiscent of their biological counterpart. We further demonstrate a proof-of-concept application of the developed methodology for dynamic information encoding in a soft substrate. We envision that this work may provide a potent approach to enable transient transduction of various chemical signals for the construction of new colloidal materials with the capability to evolve their structures and functionalities in time and space.

Facile Electret-Based Self-Powered Soft Sensor for Noncontact Positioning and Information Translation.

Noncontact sensors have demonstrated significant potential in human-machine interactions (HMIs) in terms of hygiene and less wear and tear. The development of soft, stable, and simply structured noncontact sensors is highly desired for their practical applications in HMIs. This work reports on electret-based self-powered noncontact sensors that are soft, transparent, stable, and easy to manufacture. The sensors contain a three-layer structure with a thickness of 0.34 mm that is fabricated by simply stacking a polymeric electret layer, an electrode layer, and a substrate layer together. The fabricated sensors show high charge-retention capability, keeping over 98% of the initial surface potential even after 90 h, and can accurately and repeatedly sense external approaching objects with impressive durability. The intensity of the detected signal shows a strong dependence on the distance between the object and the sensor, capable of sensing a distance as small as 2 mm. Furthermore, the sensors can report stable signals in response to external objects over 3000 cycles. By virtue of the signal dependence on distance, an intelligent noncontact positioning system is developed that can precisely detect the location of an approaching object. Finally, by integrating with eyeglasses, the transparent sensor successfully captures the movements of blinks for information translation. This work may contribute to the development of stable and easily manufactured noncontact soft sensors for HMI applications, for instance, assisting with communication for locked-in syndrome patients.