Periodic wrinkling across different scales has received considerable attention because it not only represents structure failure but also finds wide applications. How to prevent wrinkling or create desired wrinkling patterns is non-trivial because the dynamic evolution of wrinkles is a highly nonlinear problem. Herein, we report a simple yet powerful method to dynamically tune and/or erase wrinkling patterns with visible light. The light-induced photoisomerization of azobenzene units in azopolymer films leads to stress release and consequently to the erasure of the wrinkles. The wrinkles in unexposed regions are also affected and oriented perpendicular to the exposed boundary during the stress reorganization. Theoretical models were developed to understand the dynamics of the reversible photoisomerization-induced wrinkle evolution. This method can be applied for designing functional materials/devices, for example, for the reversible optical writing/erasure of information as demonstrated here.
The electrochemical nitrate reduction reaction (NO3RR) to ammonia is an essential step toward restoring the globally disrupted nitrogen cycle. In search of highly efficient electrocatalysts, tailoring catalytic sites with ligand and strain effects in random alloys is a common approach but remains limited due to the ubiquitous energy-scaling relations. With interpretable machine learning, we unravel a mechanism of breaking adsorption-energy scaling relations through the site-specific Pauli repulsion interactions of the metal d-states with adsorbate frontier orbitals. The non-scaling behavior can be realized on (100)-type sites of ordered B2 intermetallics, in which the orbital overlap between the hollow *N and subsurface metal atoms is significant while the bridge-bidentate *NO3 is not directly affected. Among those intermetallics predicted, we synthesize monodisperse ordered B2 CuPd nanocubes that demonstrate high performance for NO3RR to ammonia with a Faradaic efficiency of 92.5% at −0.5 VRHE and a yield rate of 6.25 mol h−1 g−1 at −0.6 VRHE. This study provides machine-learned design rules besides the d-band center metrics, paving the path toward data-driven discovery of catalytic materials beyond linear scaling limitations.
Here we introduce a simple low-cost yet robust method to realize spontaneously wrinkled morphologies on spherical surfaces. It is based on surface chemical oxidation of aqueous-phase-synthesized polydimethylsiloxane (PDMS) microspheres in the mixed H2SO4/HNO3/H2O solution. Consequently, curvature and overstress-sensitive wrinkles including dimples and labyrinth patterns are successfully induced on the resulting oxidized PDMS microspheres. A power-law dependence of the wrinkling wavelength on the microsphere radius exists. The effects of experimental parameters on these tunable spherical wrinkles have been systematically investigated, when the microspheres are pre-deposited on a substrate. These parameters include the radius and modulus of microspheres, the mixed acid solution composition, the oxidation duration, and the water washing post-treatment. Meanwhile, the complicated chemical oxidation process has also been well studied by in-situ optical observation via the microsphere system, which represents an intractable issue in a planar system. Furthermore, we realize surface wrinkled topographies on the whole microspheres at a large scale, when microspheres are directly dispersed in the mixed acid solution for surface oxidation. These results indicate that the introduced wet surface chemical oxidation has the great potential to apply to other complicated curved surfaces for large-scale generation of well-defined wrinkling patterns, which endow the solids with desired physical properties.
One of the grand challenges in industrial catalytic processes is the inevitable sintering and aggregation of conventional supported catalysts to large particles, leading to the decrease of activity and even deactivation with time. Herein, a surface spatial confinement strategy was employed to design high-performing catalysts for the dry reforming of methane (DRM). Specifically, active nickel (Ni) nanoparticles (NPs) were confined on the surface of a dendritic mesoporous silica (DMS) in the form of the “catalysts in coronas”. The Ni/DMS catalyst exhibited a high catalytic performance close to its equilibrium conversion (76% conversion for CH4 at 700 °C). More importantly, the prepared catalyst remained stable after 145 h time-on-stream at 700 °C without noticeable carbon deposition. This sintering and coking resistance was found to arise from the surface spatial confinement effect in which the three-dimensional dendritic layers in the corona posted a steric barrier against migration and aggregation of Ni NPs and size of Ni NPs was controlled below 5 nm, hence against sintering and coking. Meanwhile, the mesoporous feature of the layered wall facilitated mass transport of reactants to Ni species and further boosted catalysis. This strategy should be broadly applicable to a range of metal- and metal oxide-supported catalysts in high-temperature heterogeneous reactions, such as DRM, water gas shift reaction, and vehicle emission control related reactions.
Here we report a simple one-pot yet robust approach to fabricate large-scale wrinkle patterns with reversible acid-doping/base-dedoping tunability. A novel swelling-induced self-wrinkling mechanism is responsible for the in situ growth of wrinkled polyaniline (PANI) film on polydimethylsiloxane (PDMS) substrate. The spontaneously formed wrinkles with controlled microstructures such as the wavelength, spatial orientation, and location have been well regulated by PANI film thickness (via polymerization time and monomer concentration) and PDMS substrate modulus as well as the boundary conditions imposed by the substrate. The results indicate that the in situ self-wrinkling is highly desirable for patterning PANI film over large areas with the instability-driven morphologies, even in the case of curved surfaces employed. Interestingly, taking advantage of the swelling/deswelling capability via the unique acid doping/base dedoping of PANI, we have further realized unprecedented reversible modulation between the wrinkled and dewrinkled states. The involved physics underlying the complicated in situ self-wrinkling and the reversible doping/dedoping tunability has been revealed.
Mechanical instability has been shown to play an important role in the formation of wrinkle structures in biofilms, which not only can adopt instability modes as templates to regulate their 3D architectures but also can tune internal stresses to achieve stable patterns. Inspired by nature, we report a mechanical-chemical coupling method to fabricate free-standing conducting films with instability-driven hierarchical micro/nanostructured patterns. When polypyrrole (PPy) film is grown on an elastic substrate via chemical oxidation polymerization, differential growth along with in situ self-reinforcing effect induces stable wrinkle patterns with different scales of wavelengths. The self-reinforcing effect modifies the internal stresses, hence PPy films with intact wrinkles can be removed from substrates and further transferred onto target substrates for functional device fabrication. To understand the buckling mechanics, we construct a model which reveals the formation of hierarchical wrinkle patterns.
Here a simple low-cost yet robust route has been developed to prepare poly(dimethylsiloxane) (PDMS) microspheres with various surface wrinkle patterns. First, the aqueous-phase-synthesized PDMS microspheres are exposed to oxygen plasma (OP), yielding the oxidized SiOx layer and the corresponding stiff shell/compliant core system. The subsequent solvent swelling and solvent evaporation induce the spontaneous formation of a series of curvature and overstress-sensitive spherical wrinkles such as dimples, short rodlike depressions, and herringbone and labyrinth patterns. The effects of the experimental parameters, including the radius and Young's modulus of the microspheres, the OP exposure duration, and the nature of the solvents, on these tunable spherical wrinkles have been systematically studied. The experimental results reveal that a power-law dependence of the wrinkling wavelength on the microsphere radius exists. Furthermore, the induced wrinkling patterns are inherently characteristic of a memory effect and good reversibility. Meanwhile, the corresponding phase diagram of the wrinkle morphologies on the spherical surfaces vs the normalized radius of curvature and the excess swelling degree has been demonstrated. It is envisioned that the introduced strategy in principle could be applied to other curved surfaces for expeditious generation of well-defined wrinkle morphologies, which not only enables the fabrication of solids with multifunctional surface properties, but also provides important implications for the morphogenesis in soft materials and tissues.
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