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Abstract Biological organisms can perform flexible and controllable multimodal motion under external stimuli owing to the hierarchical assembly of anisotropic structures across multiple length scales. However, artificial soft actuators exhibit the limited response speed, deformation programmability and movement capability especially in harsh environments because of insufficient anisotropic hierarchy and precision in structural design. Here, we report a programmed assembly directed confinement polymerization method for the fabrication of environmentally tolerant and fast responsive hydrogels with lamellar assembly-confined cellular structure interpenetrated with highly aligned nanopillars by the directional freezing-assisted polymerization in the predesigned anisotropic laminar scaffold. The obtained hydrogel exhibits ultrafast responsiveness and anisotropic deformation exposed to temperature/light/solvent stimulation, maintaining highly consistent responsive deformation capability in all-polarity solvents over 100 days of soaking. Moreover, the hydrogels implement photoactive programmable multi-gait locomotion whose amplitude and directionality are precisely regulated by the intrinsic structure, including controlled crawling and rotation in water and non-polar solvents, and 3D self-propulsion floating and swimming in polar solvents. Thus, this hydrogel with hierarchically ordered structure and dexterous locomotion may be suitable for flexible intelligent actuators serving in harsh solvent environments.

Abstract Simultaneously improving the activity and stability of catalysts for anodic oxygen evolution reaction (OER) in proton exchange membrane water electrolysis (PEMWE) remains a notable challenge. Here, we report a chromium-doped ruthenium dioxide with oxygen vacancies, termed Cr0.2Ru0.8O2-x, that drives OER with an overpotential of 170 mV at 10 mA cm−2 and operates stably over 2000 h in acidic media. Experimental and theoretical studies show that the synergy of Cr dopant and oxygen vacancy induces an unconventional dopant-mediated hydroxyl spillover mechanism. Such dynamic hydroxyl spillover from Cr dopant to Ru active site changes the rate-determining step from OOH* formation to O2 formation and thus greatly improves the OER performance. Moreover, the Cr dopant and oxygen vacancy also play a crucial role in stabilizing surface Ru and lattice oxygen in the Ru-O-Cr structural motif. When assembled into the anode of a practical PEMWE device, Cr0.2Ru0.8O2-x enables long-term durability of over 200 h at an ampere-level current density and 60 degrees centigrade.

Abstract Investigations of one-dimensional segmented heteronanostructures (1D-SHs) have recently attracted much attention due to their potentials for applications resulting from their structure and synergistic effects between compositions and interfaces. Unfortunately, developing a simple, versatile and controlled synthetic method to fabricate 1D-SHs is still a challenge. Here we demonstrate a stress-induced axial ordering mechanism to describe the synthesis of 1D-SHs by a general under-stoichiometric reaction strategy. Using the continuum phase-field simulations, we elaborate a three-stage evolution process of the regular segment alternations. This strategy, accompanied by easy chemical post-transformations, enables to synthesize 25 1D-SHs, including 17 nanowire-nanowire and 8 nanowire-nanotube nanostructures with 13 elements (Ag, Te, Cu, Pt, Pb, Cd, Sb, Se, Bi, Rh, Ir, Ru, Zn) involved. This ordering evolution-driven synthesis will help to investigate the ordering reconstruction and potential applications of 1D-SHs.

Abstract Nanoparticles-based glues have recently been shown with substantial potential for hydrogel adhesion. Nevertheless, the transformative advance in hydrogel-based application places great challenges on the rapidity, robustness, and universality of achieving hydrogel adhesion, which are rarely accommodated by existing nanoparticles-based glues. Herein, we design a type of nanohesives based on the modulation of hydrogel mechanics and the surface chemical activation of nanoparticles. The nanohesives can form robust hydrogel adhesion in seconds, to the surface of arbitrary engineering solids and biological tissues without any surface pre-treatments. A representative application of hydrogel machine demonstrates the tough and compliant adhesion between dynamic tissues and sensors via nanohesives, guaranteeing accurate and stable blood flow monitoring in vivo. Combined with their biocompatibility and inherent antimicrobial properties, the nanohesives provide a promising strategy in the field of hydrogel based engineering.

Abstract Smart window is an attractive option for efficient heat management to minimize energy consumption and improve indoor living comfort owing to their optical properties of adjusting sunlight. To effectively improve the sunlight modulation and heat management capability of smart windows, here, we propose a co-assembly strategy to fabricate the electrochromic and thermochromic smart windows with tunable components and ordered structures for the dynamic regulation of solar radiation. Firstly, to enhance both illumination and cooling efficiency in electrochromic windows, the aspect ratio and mixed type of Au nanorods are tuned to selectively absorb the near-infrared wavelength range of 760 to 1360 nm. Furthermore, when assembled with electrochromic W18O49 nanowires in the colored state, the Au nanorods exhibit a synergistic effect, resulting in a 90% reduction of near-infrared light and a corresponding 5 °C cooling effect under 1-sun irradiation. Secondly, to extend the fixed response temperature value to a wider range of 30–50 °C in thermochromic windows, the doping amount and mixed type of W-VO2 nanowires are carefully regulated. Last but not the least, the ordered assembly structure of the nanowires can greatly reduce the level of haze and enhance visibility in the windows.

Abstract Finding highly efficient hydrogen evolution reaction (HER) catalysts is pertinent to the ultimate goal of transformation into a net-zero carbon emission society. The design principles for such HER catalysts lie in the well-known structure-property relationship, which guides the synthesis procedure that creates catalyst with target properties such as catalytic activity. Here we report a general strategy to synthesize 10 kinds of single-atom-doped CoSe2-DETA (DETA = diethylenetriamine) nanobelts. By systematically analyzing these products, we demonstrate a volcano-shape correlation between HER activity and Co atomic configuration (ratio of Co-N bonds to Co-Se bonds). Specifically, Pb-CoSe2-DETA catalyst reaches current density of 10 mA cm−2 at 74 mV in acidic electrolyte (0.5 M H2SO4, pH ~0.35). This striking catalytic performance can be attributed to its optimized Co atomic configuration induced by single-atom doping.

Abstract High-performance functional fibers play a critical role in various indispensable fields, including sensing, monitoring, and display. It is desirable yet challenging to develop conductive fibers with excellent mechanical properties for practical applications. Herein, inspired by the exquisite fascicle structure of skeletal muscle, we constructed a high-performance bacterial cellulose (BC)/carbon nanotube (CNT) conductive fiber through in situ biosynthesis and enhancement of structure and interaction. The biosynthesis strategy achieves the in situ entanglement of CNTs in the three-dimensional network of BC through the deposition of CNTs during the growth of BC. The structure enhancement through physical wet drawing and the interaction enhancement through chemical treatment facilitate orientation and bridging of components, respectively. Owing to the ingenious design, the obtained composite fibers integrate high strength (939 MPa), high stiffness (52.3 GPa), high fatigue resistance, and stable electrical performance, making them competitive for constructing fiber-based smart devices for practical applications.

The renowned mechanical performance of biological ceramics can be attributed to their hierarchical structures, wherein structural features at the nanoscale play a crucial role. However, nanoscale features, such as nanogradients, have rarely been incorporated in biomimetic ceramics because of the challenges in simultaneously controlling the material structure at multiple length scales. Here, we report the fabrication of artificial nacre with graphene oxide nanogradients in its aragonite platelets through a matrix-directed mineralization method. The gradients are formed via the spontaneous accumulation of graphene oxide nanosheets on the surface of the platelets during the mineralization process, which then induces a lateral residual stress field in the platelets. Nanoindentation tests and mercury intrusion porosimetry demonstrate that the material’s energy dissipation is enhanced both intrinsically and extrinsically through the compressive stress near the platelet surface. The energy dissipation density reaches 0.159 ± 0.007 nJ/μm3, and the toughness amplification is superior to that of the most advanced ceramics. Numerical simulations also agree with the finding that the stress field notably contributes to the overall energy dissipation. This work demonstrates that the energy dissipation of biomimetic ceramics can be further increased by integrating design principles spanning multiple scales. This strategy can be readily extended to the combinations of other structural models for the design and fabrication of structural ceramics with customized and optimized performance.

Abstract Interfacial solar steam generation (ISSG), involving the use of solar energy to evaporate water at the water‐to‐vapor interface, has presented prospects for the desalination and purification of water due to high energy conversion efficiency and low‐cost freshwater generation. Herein, inspired by the aligned nanostructure of plants for efficiently transporting nutrient ions, we optimally design and construct a biomass‐based Janus architecture evaporator with an oriented nanostructure for ISSG, using the ice template method, followed by biomimetic mineralization with the resource‐abundant and low‐cost biomass of the carboxymethyl cellulose and sodium alginate as the raw materials. Taking advantage of the oriented nanostructure allowing efficient transportation of water and coordination capacity of sodium alginate for effective enrichment of heavy‐metal ions, the biomass‐based Janus architecture shows much lower thermal conductivity and an ultrahigh steam regeneration rate of 2.3 kg m−2 h−1, considerably surpassing those of previously reported oriented biomass‐based evaporators. Moreover, the biomass precursor materials are used for this Janus evaporator, guaranteeing minimum impact on the water ecology and environment during the regeneration process of clean drinking water. This study presents an efficient, green, and sustainable pathway for ISSG to effectively achieve heavy‐metal‐free drinking water.

While polytypic semiconductors are promising for solar-to-fuel applications, preparing homojunction nanomaterials has proven challenging. Here, authors obtain a library of polytypic copper-based quaternary sulfide nanocrystals by selective epitaxial growth of kesterite phase on wurtzite structure.

Sensitive, biocompatible and stable contrast agents for MRI are in demand. Here, the authors combine gadolinium ions with amorphous calcium carbonate to make stable paramagnetic amorphous carbonate nanoclusters with high MRI contrast and significantly improved biocompatibility over commercial gadolinium-based agents.

Abstract Uncontrolled lithium dendrites seriously hinder the commercialization of lithium metal batteries in comparison to the durable lithium‐ion batteries. Herein, inspired by squashy pomegranate structure, a novel loading strategy of metallic lithium (Li) is introduced to construct dendrite‐free Li metal anodes through porous reduced graphene oxide/Au (PRGO/Au) composite microrods (MRs) as unique storage parcels. The abundant internal voids and robust host structure are capable of achieving high mass loading of Li metal and effectively alleviating the conceivable volume change during cycling, accompanied by the preferential selective plating/stripping of Li inside the graphene‐based MRs with the embedded Au nanonuclei. As a result, the obtained PRGO/Au–Li anodes deliver a long‐lifespan stable cycling up to 600 h with a high specific capacity of ≈2140 mA h g–1 and voltage hysteresis as low as 20 mV in the absence of dendrites. The assembled full cells exhibit excellent rate capability and cycling stability. This work provides an alternative strategy to construct advanced high‐energy‐density lithium batteries via the unique 1D bioinspired graphene‐based packaging strategy.

The solar conversion efficiencies of photoelectrochemical catalysis are hindered by the light harvesting range. Here, the authors use near-infrared-active photoanodes that feature lattice-matched morphological hetero-nanostructures to realize efficient photoelectrochemical hydrogen production.

Self-healing property is important for supercapacitors when powering the electronics, but designing devices that possess a universal healing mechanism remains challenging. Here, the authors achieve an optically, electrically, and magnetically-responsive self-healing device with integrated configuration.

It is desirable yet challenging to develop sustainable structural materials to replace petroleum-based plastics. Here, the authors report a facile assembly method for manufacturing high-performance structural materials with a unique combination of high strength, toughness and stiffness.

Quaternary sulfides are important candidates for solar-to-H2 conversion due to tunable bandgaps for controllable light absorption. Here, authors prepare single crystalline wurtzite Cu-Zn-In-S and Cu-Zn-Ga-S nanobelts with (0001) facets that show strong photocatalytic H2 production performances.

The lack of efficient and cost-effective catalysts for hydrogen oxidation reaction (HOR) hampers the application of hydroxide exchange membrane fuel cells. Here, authors reported bimetallic MoNi4 and WNi4 nanoalloys with marked HOR activity in alkali, among which MoNi4 outperforms the Pt/C catalyst.

Single-atom catalysts (SACs) with high metal loading are highly desired to improve catalytic performance. Here, the authors report a dual protection strategy by nanocasting SiO2 into metal–organic frameworks to prepare high-loading SACs with excellent catalytic performance toward oxygen reduction.

Abstract Plastic packaging materials are widely used because of their advantages of light weight, low cost, and convenience, especially as victuals packaging materials. Approximately 146 million metric tons of plastics were used for packaging in 2015, but most of these plastics had already been discarded and followed by serious white pollution. What's worse, the victuals packaging materials, especially polystyrene (PS) foam containers, can release microplastics (MPs) during daily usage. Through the combination of various appropriate chemical (eg, spectroscopy) and physical (eg, microscopy) characterization and analysis, the existence of MPs is proved and MPs can be intuitively observed. Although the impacts of MPs on ecosystems and human health are still under discussion, existing studies have shown that MPs can be integrated into habitats through soil transportation, affecting the health of various terrestrial invertebrates. Faced with this shocking reality, reducing the use of PS foam containers at high temperatures and developing healthy materials to substitute these plastics are promising solutions.

Summary: Due to the increasing drug resistance of bacteria and the limitations of antibacterial nanomaterials through photodynamical and photothermal routes, it is necessary to develop novel nanomaterials with outstanding enzyme-like activities and bacteria-binding capability to produce reactive oxygen species (ROS) to kill bacteria. Herein, we report the synthesis of two kinds of Cu9S5 nanoflowers composed of assemblies of nanosheets, abbreviated as Cu9S5-1 and Cu9S5-2, which possess predominantly VCuSCu and VCuSS vacancies, respectively, as confirmed by the positron annihilation spectra. Both experimental and theoretical calculation results reveal that Cu9S5-2 exhibits excellent enzyme-like activities because of stronger bacteria-binding ability and higher electron affinity that endow it with a superior antibacterial activity compared to Cu9S5-1. This study provides a deeper understanding of nanomaterials with vacancy-type-dependent enzyme-like activities and insights for the rational design of high-performance antibacterial agents in the future.

Noble-metal-free catalysts often show stability issues in acidic media due to structural degradation. Here authors show that phase-mixed engineering of cobalt diselenide electrocatalysts can enable greater covalency of Co-Se bonds and improve robustness for catalyzing hydrogen evolution in acid.

The electro-oxidative synthesis of valued chemicals offers to enhance the overall efficiency and economic viability of renewable electrosynthesis systems. Here, the authors use dopant-tuned catalysts to promote the electrosynthesis of dimethyl carbonate from CO and methanol via oxidative carbonylation.

Lithium metal is the anode of choice for the next-generation high energy density batteries. To address the key technological challenges, the authors report a hybrid Li anode design with hierarchical pores structure derived from natural diatomite and improved electrochemical performance in all-solid-state lithium batteries.

Defect-engineering offers a promising route to vary material properties and reactivities, although the achievable defect types are limited. Here, the authors introduced unusual CN-vacancies in Prussian blue analogue pre-catalysts that can limit Fe leaching and improve oxygen evolution performances.

The development of artificial muscle-like actuators is often hampered by the lack of general fabrication routes towards anisotropic responsive materials. Here, the authors fabricate anisotropic hydrogels by an in-situ polymerization strategy of a lamellar network, crosslinked by metal nanostructure assemblies.

Summary: Identifying the optimal synthetic and structural parameters in preparing pyrolyzed metal/nitrogen/carbon (M/N/C) materials is crucial for developing effective catalysts for many important catalytic processes. Here we report a group of mesoporous Co/N/C catalysts ranging from polymerized cobalt porphyrin to Co/N-doped carbons, which are prepared by pyrolysis of cobalt porphyrin using silica nanoparticles as templates at different temperatures, for boosting both heterogeneous catalysis and electrocatalysis. It is revealed that the polymerized cobalt porphyrin prepared at low temperature (500°C) is a polymer-like network with exclusive single-atom Co-Nx sites, and that the high-temperature-pyrolysis (>600°C) produces an electrically conductive Co/N-doped carbon, accompanied by part degradation of Co-Nx centers. We identify that the polymerized cobalt porphyrin with undecomposed Co-Nx centers is optimal for heterogeneous catalytic oxidation of ethylbenzene, whereas the electrically conductive Co/N-doped carbon is ideal for eletrocatalytic oxygen reduction. Our results provide new insights for rationally optimizing M/N/C catalysts for different reactions. : Chemistry; Inorganic Chemistry; Catalysis Subject Areas: Chemistry, Inorganic Chemistry, Catalysis

Summary: Designing large-area flexible transparent smart windows for high-efficiency indoor fine particulate matter (PM2.5) capture is important to guarantee safe indoor environments. In this article, we demonstrate that large-area fabrication of flexible transparent Ag-nylon mesh can be performed not only to turn the indoor light illumination intensity as thermochromic smart windows after uniformly coating with thermochromic dye but also to purify indoor air as high-efficiency PM2.5 filter. It takes only about $15.03 and 20 min to fabricate 7.5-m2 Ag-nylon flexible transparent windows without any modification with a sheet resistance of as low as 8.87 Ω sq−1 and optical transmittance of 86.05%. As an excellent PM filter (can be recycled after PM filtration), the removal efficiency is as high as 99.65% and the processing speed is high, which can reduce the PM2.5 density from heavily polluted (248 μg·m−3, purple alert) to good (32.9 μg·m−3, green statement) in 50 s. : Environmental Nanotechnology; Materials Processing; Electrical Materials Subject Areas: Environmental Nanotechnology, Materials Processing, Electrical Materials

Summary: Low density, high strength and toughness, together with good environmental stability are always desirable but hardly to achieve simultaneously for man-made structural materials. Replicating the design motifs of natural nacre clearly provides one promising route to obtain such kind of materials, but fundamental challenges remain. Herein, by choosing aramid nanofibers and mica microplatelets as building blocks, we produce a nacreous aramid-mica bulk material with a favorable combination of low density (∼1.7 g cm−3), high strength (∼387 MPa) and toughness (∼14.3 MPa m1/2), and impressive mechanical stability in some harsh environments, including acid/alkali solutions, strong ultraviolet radiation, boiling water, and liquid nitrogen, standing out from previously reported biomimetic bulk composites. Moreover, the obtained material outperforms other bulk nacre-mimetics and most engineering structural materials in terms of its specific strength (227 MPa/[Mg m−3]) and specific toughness (8.4 MPa m1/2/[Mg m−3]), making it a new promising engineering structural material for different technical fields.

Summary: Solar thermal conversion (STC) evaporation is a practical and sustainable technology for seawater desalination and sewage abatement. However, both the limited evaporation efficiency and long-term conversion stability restrain its practical application. Herein, a lotus morphology-inspired biomimetic evaporator (MBE) with Janus wettability and bimodal pores is well designed for high-rate and enduring STC evaporation. Just like lotus leaves, the hydrophobic surface of the MBE cuts off the capillarity of water, hence achieving high-efficient salt resistance and solar absorption, while the hydrophilic substance provides fast water transportation. The bimodal-pore structures formed by incorporating lotus root-like mesopores into the 3D truss-like macropores effectively decrease density and thermal conductivity for self-floating and thermal regulation. This results in a low water vaporization enthalpy of 1846 J g−1, leading to a much higher evaporation rate at the same conversion efficiency. This work may open new avenues for developing high-performance evaporation systems.

The precise control over nanoscale structures is crucial in developing new, functional nanomaterials. Here, authors demonstrate a controllable method to epitaxially stack CdS quantum dots into ZnS nanowires and show improved photocatalytic hydrogen evolution activities.

Summary: Cobalt diselenide (CoSe2) has been demonstrated to be an efficient and economic electrocatalyst for oxygen evolution reaction (OER) both experimentally and theoretically. However, the catalytic performance of up-to-now reported CoSe2-based OER catalysts is still far below commercial expectation. Herein, we report a hybrid catalyst consisting of CoSe2 nanosheets grafted on defective graphene (DG). This catalyst exhibits a largely enhanced OER activity and robust stability in alkaline solution (overpotential at 10 mA cm−2: 270 mV; Tafel plots: 64 mV dec−1). Both experimental evidence and density functional theory calculations reveal that the outstanding OER performance of this hybrid catalyst can be attributed to the synergetic effect of exposed cobalt atoms and carbon defects (electron transfer from CoSe2 layer to defect sites at DG). Our results suggest a promising way for the development of highly efficient and low-cost OER catalysts based on transition metal dichalcogenides. : Catalysis; Chemistry; Energy Materials Subject Areas: Catalysis, Chemistry, Energy Materials

Biomimetic assembly of nanosheets into nacre-like structures and films is of interest for a range of applications; the abundance of mica makes it a good candidate. Here, the authors report on the large-scale exfoliation of ground mica into nanosheets and the assembly into polymeric mica films.

Stretchable conductors are important for further developments in the electronics industry, but improving the deformability when maintaining the high-level conductivity is still challenging. Here the authors demonstrate a ternary self-healing silver nanowire/polymer network as high-performance stretchable conductor.

Transition metal dichalcogenides represent an exciting class of earth-abundant hydrogen-from-water electrocatalysts, although low efficiencies limit commercialization. Here, authors present a doping strategy to induce a phase transition in cobalt selenide and boost H2-evolution performance.

Artificial materials that replicate the mechanical properties of nacre represent important structural materials, but are difficult to produce in bulk. Here, the authors exploit the bottom-up assembly of 2D nacre-mimetic films to fabricate 3D bulk artificial nacre with an optimized architecture and excellent mechanical properties.