Hierarchical Graphene Foam for Efficient Omnidirectional Solar–Thermal Energy Conversion

Efficient solar–thermal energy conversion is essential for the harvesting and transformation of abundant solar energy, leading to the exploration and design of efficient solar–thermal materials. Carbon‐based materials, especially graphene, have the advantages of broadband absorption and excellent photothermal properties, and hold promise for solar–thermal energy conversion. However, to date, graphene‐based solar–thermal materials with superior omnidirectional light harvesting performances remain elusive. Herein, hierarchical graphene foam (h‐G foam) with continuous porosity grown via plasma‐enhanced chemical vapor deposition is reported, showing dramatic enhancement of broadband and omnidirectional absorption of sunlight, which thereby can enable a considerable elevation of temperature. Used as a heating material, the external solar–thermal energy conversion efficiency of the h‐G foam impressively reaches up to ≈93.4%, and the solar–vapor conversion efficiency exceeds 90% for seawater desalination with high endurance.     

Solution‐Processed All‐Ceramic Plasmonic Metamaterials for Efficient Solar–Thermal Conversion over 100–727 °C

Low‐cost and large‐area solar–thermal absorbers with superior spectral selectivity and excellent thermal stability are vital for efficient and large‐scale solar–thermal conversion applications, such as space heating, desalination, ice mitigation, photothermal catalysis, and concentrating solar power. Few state‐of‐the‐art selective absorbers are qualified for both low‐ ( < 200  ° C) and high‐temperature ( > 600  ° C) applications due to insufficient spectral selectivity or thermal stability over a wide temperature range. Here, a high‐performance plasmonic metamaterial selective absorber is developed by facile solution‐based processes via assembling an ultrathin ( ≈ 120 nm) titanium nitride (TiN) nanoparticle film on a TiN mirror. Enabled by the synergetic in‐plane plasmon and out‐of‐plane Fabry–Pérot resonances, the all‐ceramic plasmonic metamaterial simultaneously achieves high, full‐spectrum solar absorption (95%), low mid‐IR emission (3% at 100  ° C), and excellent stability over a temperature range of 100–727  ° C, even outperforming most vacuum‐deposited absorbers at their specific operating temperatures. The competitive performance of the solution‐processed absorber is accompanied by a significant cost reduction compared with vacuum‐deposited absorbers. All these merits render it a cost‐effective, universal solution to offering high efficiency (89–93%) for both low‐ and high‐temperature solar–thermal applications.     

Molecular Design of Polymer Heterojunctions for Efficient Solar–Hydrogen Conversion

Semiconducting photocatalytic solar–hydrogen conversion (SHC) from water is a great challenge for renewable fuel production. Organic semiconductors hold great promise for SHC in an economical and environmentally benign manner. However, organic semiconductors available for SHC are scarce and less efficient than most inorganic ones, largely due to their intrinsic Frenkel excitons with high binding energy. In this study the authors report polymer heterojunction (PHJ) photocatalysts consisting of polyfluorene family polymers and graphitic carbon nitride (g‐C₃N₄) for efficient SHC. A molecular design strategy is executed to further promote the exciton dissociation or light harvesting ability of these PHJs via alternative approaches. It is revealed that copolymerizing electron‐donating carbazole unit into the poly(9,9‐dioctylfluorene) backbone promotes exciton dissociation within the poly(N‐decanyl‐2,7‐carbazole‐alt‐9,9‐dioctylfluorene) (PCzF)/g‐C₃N₄ PHJ, achieving an enhanced apparent quantum yield (AQY) of 27% at 440 nm over PCzF/g‐C₃N₄. Alternatively, copolymerizing electron‐accepting benzothiadiazole unit extended the visible light response of the obtained poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole)/g‐C₃N₄ PHJ, leading to an AQY of 13% at 500 nm. The present study highlights that constructing PHJs and adapting a rational molecular design of PHJs are effective strategies to exploit more of the potential of organic semiconductors for efficient solar energy conversion.     

Scalable, “Dip‐and‐Dry” Fabrication of a Wide‐Angle Plasmonic Selective Absorber for High‐Efficiency Solar–Thermal Energy Conversion

A galvanic‐displacement‐reaction‐based, room‐temperature “dip‐and‐dry” technique is demonstrated for fabricating selectively solar‐absorbing plasmonic‐nanoparticle‐coated foils (PNFs). The technique, which allows for facile tuning of the PNFs' spectral reflectance to suit different radiative and thermal environments, yields PNFs which exhibit excellent, wide‐angle solar absorptance (0.96 at 15°, to 0.97 at 35°, to 0.79 at 80°), and low hemispherical thermal emittance (0.10) without the aid of antireflection coatings. The thermal emittance is on par with those of notable selective solar absorbers (SSAs) in the literature, while the wide‐angle solar absorptance surpasses those of previously reported SSAs with comparable optical selectivities. In addition, the PNFs show promising mechanical and thermal stabilities at temperatures of up to 200 °C. Along with the performance of the PNFs, the simplicity, inexpensiveness, and environmental friendliness of the “dip‐and‐dry” technique makes it an appealing alternative to current methods for fabricating selective solar absorbers.     

Self‐Organized Graphene Nanosheets with Corrugated,Ordered Tip Structures for High‐Performance Flexible Field Emission

Patterned reduced graphene oxide (rGO) films with vertically aligned tip structures are fabricated by a straightforward self‐assembly method. The size, uniformity of the patterns, and alignment of the tips are successfully controlled according to the concentration of a GO/octadecylamine (ODA)‐dispersed solution. The surface energy difference between the GO/ODA solution and a self‐assembled water droplet is a critical parameter for determining the pattern structure. Numerous rGO nanosheets are formed so as to be vertically aligned with respect to the substrate during film fabrication at GO concentrations below 2.0 g/L. These samples provide high field‐emission characteristics. The patterned rGO arrays are highly flexible with preservation of the field emission properties, even at large bending angles. This is attributed to the high crystallinity, emitter density, and good chemical stability of the rGO arrays, as well as the strong interactions between the rGO arrays and the substrate.     

MOF‐Based Hierarchical Structures for Solar‐Thermal Clean Water Production

Solar‐thermal water evaporation, as a promising method for clean water production, has attracted increasing attention. However, solar water evaporators that exhibit both high water vapor generation ability and anti‐oil‐fouling ability have not been reported. Here, a unique metal–organic‐framework‐based hierarchical structure, referred to as MOF‐based hierarchical structure (MHS), is rationally designed and prepared, which simultaneously displays a high solar absorption and a superhydrophilic and underwater superoleophobic surface property. As a proof‐of‐concept application, a device prepared from the MHS can achieve a high solar‐thermal water evaporation rate of 1.50 kg m^?2 h^?1 under 1 sun illumination. Importantly, the MHS also possesses an excellent anti‐oil‐fouling property, ensuring its superior water evaporation performance even in oil‐contaminated water. The high solar‐thermal water evaporation rate and anti‐oil‐fouling property make the MHS a promising material for the solar‐thermal water production.     

Co Nanoislands Rooted on Co–N–C Nanosheets as Efficient Oxygen Electrocatalyst for Zn–Air Batteries

Developing non‐precious‐metal bifunctional oxygen reduction and evolution reaction (ORR/OER) catalysts is a major task for promoting the reaction efficiency of Zn–air batteries. Co‐based catalysts have been regarded as promising ORR and OER catalysts owing to the multivalence characteristic of cobalt element. Herein, the synthesis of Co nanoislands rooted on Co–N–C nanosheets supported by carbon felts (Co/Co–N–C) is reported. Co nanosheets rooted on the carbon felt derived from electrodeposition are applied as the self‐template and cobalt source. The synergistic effect of metal Co islands with OER activity and Co–N–C nanosheets with superior ORR performance leads to good bifuctional catalytic performances. Wavelet transform extended X‐ray absorption fine spectroscopy and X‐ray photoelectron spectroscopy certify the formation of Co (mainly Co⁰) and the Co–N–C (mainly Co²⁺ and Co³⁺) structure. As the air‐cathode, the assembled aqueous Zn–air battery exhibits a small charge–discharge voltage gap (0.82 V@10 mA cm^?2) and high power density of 132 mW cm^?2, outperforming the commercial Pt/C catalyst. Additionally, the cable flexible rechargeable Zn–air battery exhibits excellent bendable and durability. Density functional theory calculation is combined with operando X‐ray absorption spectroscopy to further elucidate the active sites of oxygen reactions at the Co/Co–N–C cathode in Zn–air battery.     

Cationic Copolymer‐Chaperoned 2D–3D Reversible Conversion of Lipid Membranes

Nanosheets have thicknesses on the order of nanometers and planar dimensions in the micrometer range. Nanomaterials that are capable of converting reversibly between 2D nanosheets and 3D structures in response to specific triggers can enable construction of nanodevices. Supra‐molecular lipid nanosheets and their triggered conversions to 3D structures including vesicles and cups are reported. They are produced from lipid vesicles upon addition of amphiphilic peptides and cationic copolymers that act as peptide chaperones. By regulation of the chaperoning activity of the copolymer, 2D to 3D conversions are reversibly triggered, allowing tuning of lipid bilayer structures and functionalities.     

Freestanding 1T‐MnxMo1–xS2–ySey and MoFe2S4–zSez Ultrathin Nanosheet‐Structured Electrodes for Highly Efficient Flexible Solid‐State Asymmetric Supercapacitors

Fabrication of hierarchical nanosheet arrays of 1T phase of transition‐metal dichalcogenides is indeed a critical task, but it holds immense potential for energy storage. A single‐step strategy is employed for the fabrication of stable 1T‐Mn_xMo_1–xS_2–ySe_y and MoFe₂S_4–zSe_z hierarchical nanosheet arrays on carbon cloth as positive and negative electrodes, respectively. The flexible asymmetric supercapacitor constructed with these two electrodes exhibits an excellent electrochemical performance (energy density of ≈69 Wh kg^?1 at a power density of 0.985 kW kg^?1) with ultralong cyclic stability of ≈83.5% capacity retention, after 10 000 consecutive cycles. Co‐doping of the metal and nonmetal boosts the charge storage ability of the transition‐metal chalcogenides following enrichment in the metallic 1T phase, improvement in the surface area, and expansion in the interlayer spacing in tandem, which is the key focus of the present study. This study explicitly demonstrates the exponential enhancement of specific capacity of MoS₂ following intercalation and doping of Mn and Se, and Fe₂S₃ following doping of Mo and Se could be an ideal direction for the fabrication of novel energy‐storage materials with high‐energy storage ability.     

Self‐Catalyzed Growth of Co–N–C Nanobrushes for Efficient Rechargeable Zn–Air Batteries

Highly efficient and stable bifunctional electrocatalysts for oxygen reduction and evolution are essential for aqueous rechargeable Zn–air batteries, which require highly active sites as well as delicate structural design for increasing effective active sites and facilitating mass/electron transfer. Herein, a scalable and facile self‐catalyzed growth strategy is developed to integrate highly active Co–N–C sites with 3D brush‐like nanostructure, achieving Co–N–C nanobrushes with Co,N‐codoped carbon nanotube branches grown on Co,N‐codoped nanoparticle assembled nanowire backbones. Systematic investigations suggest that nanobrushes deliver significantly improved electrocatalytic activity compared with nanowire or nanotube counterparts and the longer nanotube branches give the better performance. Benefiting from the increase of accessible highly active sites and enhanced mass transfer and electron transportation, the present Co–N–C nanobrush exhibits superior electrocatalytic activity and durability when used as a bifunctional oxygen catalyst. It enables a rechargeable Zn–air battery with a high peak power density of 246 mW cm^?2 and excellent cycling stability. These results suggest that the reported synthetic strategy may open up possibilities for exploring efficient electrocatalysts for diverse applications.     

One‐Step In Situ Growth of Iron–Nickel Sulfide Nanosheets on FeNi Alloy Foils: High‐Performance and Self‐Supported Electrodes for Water Oxidation

Efficient and durable oxygen evolution reaction (OER) catalysts are highly required for the cost‐effective generation of clean energy from water splitting. For the first time, an integrated OER electrode based on one‐step direct growth of metallic iron–nickel sulfide nanosheets on FeNi alloy foils (denoted as Fe? Ni₃S₂/FeNi) is reported, and the origin of the enhanced OER activity is uncovered in combination with theoretical and experimental studies. The obtained Fe? Ni₃S₂/FeNi electrode exhibits highly catalytic activity and long‐term stability toward OER in strong alkaline solution, with a low overpotential of 282 mV at 10 mA cm^?2 and a small Tafel slope of 54 mV dec^?1. The excellent activity and satisfactory stability suggest that the as‐made electrode provides an attractive alternative to noble metal‐based catalysts. Combined with density functional theory calculations, exceptional OER performance of Fe? Ni₃S₂/FeNi results from a combination of efficient electron transfer properties, more active sites, the suitable O₂ evolution kinetics and energetics benefited from Fe doping. This work not only simply constructs an excellent electrode for water oxidation, but also provides a deep understanding of the underlying nature of the enhanced OER performance, which may serve as a guide to develop highly effective and integrated OER electrodes for water splitting.     

Silk‐Derived 2D Porous Carbon Nanosheets with Atomically‐Dispersed Fe‐Nx‐C Sites for Highly Efficient Oxygen Reaction Catalysts

Controlled synthesis of highly efficient, stable, and cost‐effective oxygen reaction electrocatalysts with atomically‐dispersed Me–N_x–C active sites through an effective strategy is highly desired for high‐performance energy devices. Herein, based on regenerated silk fibroin dissolved in ferric chloride and zinc chloride aqueous solution, 2D porous carbon nanosheets with atomically‐dispersed Fe–N_x–C active sites and very large specific surface area (≈2105 m² g^?1) are prepared through a simple thermal treatment process. Owing to the 2D porous structure with large surface area and atomic dispersion of Fe–N_x–C active sites, the as‐prepared silk‐derived carbon nanosheets show superior electrochemical activity toward the oxygen reduction reaction with a half‐wave potential (E_1/2) of 0.853 V, remarkable stability with only 11 mV loss in E_1/2 after 30 000 cycles, as well as good catalytic activity toward the oxygen evolution reaction. This work provides a practical and effective approach for the synthesis of high‐performance oxygen reaction catalysts towards advanced energy materials.     

High‐Performance Integrated Self‐Package Flexible Li–O2 Battery Based on Stable Composite Anode and Flexible Gas Diffusion Layer

With the rising development of flexible and wearable electronics, corresponding flexible energy storage devices with high energy density are required to provide a sustainable energy supply. Theoretically, rechargeable flexible Li–O₂ batteries can provide high specific energy density; however, there are only a few reports on the construction of flexible Li–O₂ batteries. Conventional flexible Li–O₂ batteries possess a loose battery structure, which prevents flexibility and stability. The low mechanical strength of the gas diffusion layer and anode also lead to a flexible Li–O₂ battery with poor mechanical properties. All these attributes limit their practical applications. Herein, the authors develop an integrated flexible Li–O₂ battery based on a high‐fatigue‐resistance anode and a novel flexible stretchable gas diffusion layer. Owing to the synergistic effect of the stable electrocatalytic activity and hierarchical 3D interconnected network structure of the free‐standing cathode, the obtained flexible Li–O₂ batteries exhibit superior electrochemical performance, including a high specific capacity, an excellent rate capability, and exceptional cycle stability. Furthermore, benefitting from the above advantages, the as‐fabricated flexible batteries can realize excellent mechanical and electrochemical stability. Even after a thousand cycles of the bending process, the flexible Li–O₂ battery can still possess a stable open‐circuit voltage, a high specific capacity, and a durable cycle performance.