Highly Porous Yet Transparent Mechanically Flexible Aerogels Realizing Solar-Thermal Regulatory Cooling

The demand for highly porous yet transparent aerogels with mechanical flexibility and solar-thermal dual-regulation for energy-saving windows is significant but challenging.Herein,a delaminated aerogel film(DAF)is fabricated through filtration-induced delaminated gelation and ambient drying.The delaminated gelation process involves the assembly of fluorinated cellulose nanofiber(FCNF)at the solid-liquid interface between the filter and the filtrate during filtration,resulting in the formation of lamellar FCNF hydrogels with strong intra-plane and weak interlayer hydrogen bonding.By exchanging the solvents from water to hexane,the hydrogen bonding in the FCNF hydrogel is further enhanced,enabling the formation of the DAF with intra-layer mesopores upon ambient drying.The resulting aerogel film is lightweight and ultra-flexible,which pos-sesses desirable properties of high visible-light transmittance(91.0%),low thermal conductivity(33 mW m^(-1) K^(-1)),and high atmospheric-window emissivity(90.1%).Furthermore,the DAF exhibits reduced surface energy and exceptional hydrophobicity due to the presence of fluorine-containing groups,enhancing its durability and UV resistance.Consequently,the DAF has demonstrated its potential as solar-thermal regulatory cooling window materials capable of simultaneously providing indoor lighting,thermal insulation,and daytime radiative cooling under direct sunlight.Significantly,the enclosed space protected by the DAF exhibits a temperature reduction of 2.6℃ compared to that shielded by conventional architectural glass.

Plasma-assisted aerogel interface engineering enables uniform Zn^(2+)flux and fast desolvation kinetics toward zinc metal batteries

The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.

Thermally Conductive and UV-EMI Shielding Electronic Textiles for Unrestricted and Multifaceted Health Monitoring

Skin-attachable electronics have garnered considerable research attention in health monitoring and artificial intelligence domains,whereas susceptibility to elec-tromagnetic interference(EMI),heat accumulation issues,and ultraviolet(UV)-induced aging problems pose significant constraints on their potential applications.Here,an ultra-elas-tic,highly breathable,and thermal-comfortable epidermal sensor with exceptional UV-EMI shielding performance and remarkable thermal conductivity is developed for high-fidelity monitoring of multiple human electrophysiological signals.Via filling the elastomeric microfibers with thermally conductive boron nitride nanoparticles and bridging the insulating fiber interfaces by plating Ag nanoparticles(NPs),an interwoven thermal con-ducting fiber network(0.72 W m^(-1) K^(-1))is constructed benefiting from the seamless thermal interfaces,facilitating unimpeded heat dissipation for comfort skin wearing.More excitingly,the elastomeric fiber substrates simultaneously achieve outstanding UV protection(UPF=143.1)and EMI shielding(SET>65,X-band)capabilities owing to the high electrical conductivity and surface plasmon resonance of Ag NPs.Furthermore,an electronic textile prepared by printing liquid metal on the UV-EMI shielding and thermally conductive nonwoven textile is finally utilized as an advanced epidermal sensor,which succeeds in monitoring different electrophysiological signals under vigorous electromagnetic interference.This research paves the way for developing protective and environmentally adaptive epidermal electronics for next-generation health regulation.

d-d Orbital coupling induced by crystal-phase engineering assists acetonitrile electroreduction to ethylamine

The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.

Correction to:Highly Porous Yet Transparent Mechanically Flexible Aerogels Realizing Solar-Thermal Regulatory Cooling

Tianxi Liu was missed to be denoted as a corresponding author in the article.Both Chao Zhang and Tianxi Liu are the corresponding authors of this article.The original article has been corrected.Open Access This article is licensed under a Creative Commons Attribution 4.0 International License,which permits use,sharing,adaptation,distribution,and reproduction in any medium or format,as long as you give appropriate credit to the original author(s)and the source,provide a link to the Creative Commons licence,and indicate if changes were made.The images or other third-party material in this article are included in the article’s Creative Commons licence,unless indicated otherwise in a credit line to the material.If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use,you will need to obtain permission directly from the copyright holder.

3D Printed Integrated Gradient-Conductive MXene/CNT/Polyimide Aerogel Frames for Electromagnetic Interference Shielding with Ultra-Low Reflection

Construction of advanced electromagnetic interference(EMI)shielding materials with miniaturized,programmable structure and low reflection are promising but challenging.Herein,an integrated transition-metal carbides/carbon nanotube/polyimide(gradient-conductive MXene/CNT/PI,GCMCP)aerogel frame with hierarchical porous structure and gradient-conductivity has been constructed to achieve EMI shielding with ultra-low reflection.The gradient-conductive structures are obtained by continuous 3D printing of MXene/CNT/poly(amic acid)inks with different CNT contents,where the slightly conductive top layer serves as EM absorption layer and the highly conductive bottom layer as reflection layer.In addition,the hierarchical porous structure could extend the EM dissipation path and dissipate EM by multiple reflections.Consequently,the GCMCP aerogel frames exhibit an excellent average EMI shielding efficiency(68.2 dB)and low reflection(R=0.23).Furthermore,the GCMCP aerogel frames with miniaturized and programmable structures can be used as EMI shielding gaskets and effectively block wireless power transmission,which shows a prosperous application prospect in defense industry and aerospace.

Superelastic Radiative Cooling Metafabric for Comfortable Epidermal Electrophysiological Monitoring

Epidermal electronics with superb passive-cooling capabilities are of great value for both daytime outdoor dressing comfort and low-carbon economy. Herein, a multifunctional and skinattachable electronic is rationally developed on a porous all-elastomer metafabric for efficient passive daytime radiative cooling(PDRC) and human electrophysiological monitoring. The cooling characteristics are realized through the homogeneous impregnation of polytetrafluoroethylene microparticles in the styrene–ethylene–butylene–styrene fibers, and the rational regulation of microporosity in SEBS/PTFE metafabrics, thus synergistically backscatter ultraviolet–visible–near-infrared light(maximum reflectance over 98.0%) to minimize heat absorption while efficiently emit human-body midinfrared radiation to the sky. As a result, the developed PDRC metafabric achieves approximately 17℃ cooling effects in an outdoor daytime environment and completely retains its passive cooling performance even under 50% stretching. Further, high-fidelity electrophysiological monitoring capability is also implemented in the breathable and skin-conformal metafabric through liquid metal printing, enabling the accurate acquisition of human electrocardiograph, surface electromyogram, and electroencephalograph signals for comfortable and lengthy health regulation. Hence, the fabricated superelastic PDRC metafabric opens a new avenue for the development of body-comfortable electronics and low-carbon wearing technologies.

High Fe^(LS)(C)electrochemical activity of an iron hexacyanoferrate cathode boosts superior sodium ion storage

Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.

Mo/Fe bimetallic pyrophosphates derived from Prussian blue analogues for rapid electrocatalytic oxygen evolution

Efficient and stable oxygen evolution electrocatalysts are indispensable for industrial applications of water splitting and hydrogen production.Herein,a simple and practical method was applied to fabricate(Mo,Fe)P2O7@NF electrocatalyst by directly growing Mo/Fe bimetallic pyrophosphate derived from Prussian blue analogues on three-dimensional porous current collector.In alkaline media,the developed material possesses good hydrophilic features and exhibits best-in-class oxygen evolution reaction(OER)performances.Surprisingly,the(Mo,Fe)P_(2)O_(7)@NF only requires overpotentials of 250 and 290 mV to deliver 100 and 600 mA cm^(-2)in 1 mol L^(-1)KOH,respectively.Furthermore,the(Mo,Fe)P_(2)O_(7)@NF shows outstanding performances in alkaline salty water and 1 mol L^(-1)high purity KOH.A worthwhile pathway is provided to combine bimetallic pyrophosphate with commercial Ni foam to form robust electrocatalysts for stable electrocatalytic OER,which has a positive impact on both hydrogen energy application and environmental restoration.

Modulating Pd e_(g) orbital occupancy in Pd-Au metallic aerogels for efficient carbon dioxide reduction

The electronic structure of electrocatalysts plays a critical role in energy conversion,whereas for an efficient catalyst,it is challenging to modulate the orbitals.Herein,we present a new strategy to modulate the e_(g) orbital occupancy of Pd by constructing composition-controllable Pd-Au metallic aerogels(MAs),optimizing the d-band center of Pd to achieve excellent performance for electrochemical carbon dioxide reduction reaction(CO_(2)RR).Specifically,Pd_(1)Au_(2) MAs achieve almost 100% Faraday efficiency(FE) of CO in the range of-0.40 to-0.80 V vs.reversible hydrogen electrode(RHE),as well as the long-term stability,being one of the best Pd-based materials for CO_(2)RR.The X-ray photoelectron spectroscopy(XPS) results and density functional theory(DFT) calculations demonstrate that the introduction of Au modulates the Pd e_(g) orbital occupancy,which significantly weakens *CO adsorption on Pd,reduces the CO_(2)RR energy barrier and consequently improves the electrocatalytic activity and stability for long-term applications.Our work highlights a new strategy for designing efficient electrocatalysts for CO_(2)RR and beyond.

Polyimide separators for rechargeable batteries

Separators are indispensable components of modern electrochemical energy storage devices such as lithium-ion batteries(LIBs).They perform the critical function of physically separating the electrodes to prevent short-circuits while permitting the ions to pass through.While conventional separators using polypropylene(PP) and polyethylene(PE) are prone to shrinkage and melting at relatively high temperatures(150℃ or above) causing short circuits and thermal runaway,separators made of thermally stable polyimides(PIs) are electrochemically stable and resistant to high temperatures,and possess good mechanical strength-making them a promising solution to the safety concerns of LIBs.In this review,the research progress on PI separators for use in LIBs is summarized with a special focus on molecular design and microstructural control.In view of the significant progress in advanced chemistries beyond LIBs,recent advances in PI-based membranes for applications in lithium-sulfur,lithium-metal,and solid-state batteries are also reviewed.Finally,practical issues are also discussed along with their prospects.

Structural engineering of cathodes for improved Zn-ion batteries

Aqueous zinc-ion batteries(ZIBs) are attracting considerable attention because of their low cost,high safety and abundant anode material resources.However,the major challenge faced by aqueous ZIBs is the lack of stable and high capacity cathode materials due to their complicated reaction mechanism and slow Zn-ion transport kinetics.This study reports a unique 3 D ’flower-like’ zinc cobaltite(ZnCo_(2)O_(4-x)) with enriched oxygen vacancies as a new cathode material for aqueous ZIBs.Computational calculations reveal that the presence of oxygen vacancies significantly enhances the electronic conductivity and accelerates Zn^(2+) diffusion by providing enlarged channels.The as-fabricated batteries present an impressive specific capacity of 148.3 mAh g^(-1) at the current density of 0.05 A g^(-1),high energy(2.8 Wh kg^(-1)) and power densities(27.2 W kg^(-1)) based on the whole device,which outperform most of the reported aqueous ZIBs.Moreover,a flexible solid-state pouch cell was demonstrated,which delivers an extremely stable capacity under bending states.This work demonstrates that the performance of Zn-ion storage can be effectively enhanced by tailoring the atomic structure of cathode materials,guiding the development of low-cost and eco-friendly energy storage materials.

Free-standing flexible graphene-based aerogel film with high energy density as an electrode for supercapacitors

Two-dimensional graphene film exhibits sluggish ion diffusivity while three-dimensional(3D)graphene aerogel has low packing density and poor mechanical flexibility.Consequently,there is an urgent need for graphenebased film with both mechanical robustness and high specific capacitance.Here,we present an easy and scalable strategy for fabricating a free-standing flexible graphene-based aerogel film electrode with a two-layered structure,in which the top layer is an interconnected macroporous reduced graphene oxide/carbon nanotube(RGO/CNT)aerogel,and the bottom layer is a flexible electrospun polyacrylonitrile(PAN)nanofiber membrane.The porous 3D structure of the aerogel provides fast transport of electrolyte ions and electrons,while the nanofiber membrane provides both strong support for the aerogel and mechanical flexibility.Polypyrrole(PPy)can be uniformly loaded on RGO/CNT/PAN(RCP)composite aerogel film to provide pseudocapacitance,and nitrogen-doped RGO/CNT/carbon nanofiber(NRCC)aerogel film can be obtained by further pyrolysis.The resultant RCP@PPy-0.05//NRCC based asymmetric supercapacitor can have a maximum voltage of 1.7 V and a maximum energy density of 60.6 W h kg^(-1)at 850.2 W kg^(-1).This indicates that free-standing graphene-based aerogel film can be used in flexible supercapacitors.

Interface-induced polymerization strategy for constructing titanium dioxide embedded carbon porous framework with enhanced chemical immobilization towards lithium polysulfides

The shuttle effect induced by soluble lithium polysulfides(LiPSs)is known as one of the crucial issues that limit the practical applications of lithium-sulfur(Li-S)batteries.Herein,a titanium dioxide nanoparticle embedded in nitrogen-doped porous carbon nanofiber(TiO_(2)@NCNF)composite is constructed via an interface-induced polymerization strategy to serve as an ideal sulfur host.Under the protection of the nanofiber walls,the uniformly dispersed TiO_(2) nanocrystalline can act as capturing centers to constantly immobilize LiPSs towards durable sulfur chemistry.Besides,the mesoporous microstructure in the fibrous framework endows the TiO_(2)@NCNF host with strong physical reservation for sulfur and LiPSs,sufficient pathways for electron/ion transfer,and excellent endurance for volume change.As expected,the sulfur-loaded TiO_(2)@NCNF composite electrode presents a fabulous rate performance and long cycle lifespan(capacity fading rate of 0.062%per cycle over 500 cycles)at 2.0 C.Furthermore,the assembled Li-S batteries harvest superb areal capacity and cycling stability even under high sulfur loading and lean electrolyte conditions.

3D Printed Polyimide/Silica Composite Aerogels for Customizable Thermal Insulation from-50℃ to 1300℃

Aerogels are widely used as thermal insulation materials because of their high porosity and low bulk density.However,the insulation performance of aerogels is limited to a narrow temperature range.Besides,the preparation of aerogel materials with precisely controlled and complex architectures is still challenging.Here,we report 3D printed polyimide/silica aerogel particle(PI/SAP)composite aerogels for thermal insulation in a wide range of temperature with customized applications.The printability and shape fidelity of 3D printed composite aerogels is improved by adding hydrophilic SAP as a rheology modifier.The resulting PI/SAP composite aerogel exhibits excellent flame-retardant properties and thermal insulation from-50℃ to 1300℃.Moreover,the PI/SAP composite aerogel with customized shape can be applied for battery insulation at subzero temperatures,promising to be used as customizable and stable insulating materials in a variety of complex and extreme applications.

A Radiative-Cooling Hierarchical Aligned Porous Poly(vinylidene fluoride)Film by Freeze-Thaw-Promoted Nonsolvent-Induced Phase Separation

Passive daytime radiative cooling(PDRC)is an innovative and sustainable cooling technology that holds immense potential for addressing the energy crisis.Despite the numerous reports on radiative coolers,the design of a straightforward,efficient,and readily producible system remains a challenge.Herein,we present the development of a hierarchical aligned porous poly(vinylidene fluoride)(HAP-PVDF)film through a freeze-thaw-promoted nonsolvent-induced phase separation strategy.This film features oriented microporous arrays in conjunction with random nanopores,enabling efficient radiative cooling performance under direct sunlight conditions.The incorporation of both micro-and nano-pores in the HAP-PVDF film results in a remarkable solar reflectance of 97%and a sufficiently high infrared thermal emissivity of 96%,facilitating sub-environmental cooling at 18.3℃ on sunny days and 13.1℃ on cloudy days.Additionally,the HAP-PVDF film also exhibits exceptional flexibility and hydrophobicity.Theoretical calculations further confirm a radiative cooling power of 94.8 W·m^(-2)under a solar intensity of 1000W·m^(-2),demonstrating a performance comparable to the majority of reported radiative coolers.

Asymmetric fireproof gel polymer electrolyte constructed by boron-contained covalent organic framework for dendrite-free sodium metal battery

Gel polymer electrolytes (GPEs) with flexibility, easy processability, and low cost have been regarded as promising alternatives for conventional liquid electrolytes in next-generation sodium metal batteries (SMBs). However, GPEs often suffer from combustion risk and inferior interfacial compatibility toward Na metal anode, which severely limit their wide commercial applications. Here, a rational design of asymmetric fireproof GPE (AFGPE) modified with a boron-contained covalent organic framework (BCOF) on one side is developed through in-situ crosslinking polymerization process. Benefiting from the unique structure and composition, the resulting AFGPE exhibits high Na+ transference number, wide electrochemical window, excellent mechanical properties and high safety. Especially, the nanoscale BCOF layer with uniform nanochannels works as ion sieve that homogenizes Na+ flux during Na plating process, while the abundant Lewis-acid B sites can strongly capture counter anions and decrease space charge layer at anode side, thus promoting the uniform Na deposition to effectively suppress dendrite growth. Consequently, the Na/AFGPE/Na symmetric cells demonstrate remarkable cycling stability for over 1200 h at 0.1 mA·cm^(-2), and the solid-state SMBs exhibit outstanding cycling properties and rate capability, delivering a high capacity retention of 96.4% under current density of 1 C for over 1000 cycles.

Advancing Energy Systems with In-Situ and Operando Surface-Enhanced Raman Scattering Spectroscopy

Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and operando SERS in energy-related research,highlighting its unique capabilities and significant contributions to understanding energy storage and conversion processes.We first introduce the fundamental principles of SERS,key SERS-derived techniques,and commonly employed platforms.Subsequently,we delve into the diverse applications of in-situ and operando SERS across various energy systems,encompassing photocatalytic and electrocatalytic systems,fuel cells,solar cells,and batteries.Finally,we conclude with our perspective on the current challenges and prospects in this area.We hope thismini-review serves as an essential overview to guide the design and implementation of in-situ and operando SERS studies of energy systems.

Fluorine-containing polyimide nanofiber membranes for durable and anti-aging daytime radiative cooling

Personal daytime radiative cooling(PDRC)materials have high sunlight reflection and high selective emis-sivity to outer space in the main atmospheric window,demonstrating huge potential in energy-saving for sustainable development.Recently,polymer-based membranes for radiative cooling have been widely re-ported,due to their easy processing,low cost,and unique optical performance.However,the desired high sunlight reflectance of PDRC materials is easily dampened by environmental aging,high temperature,and ultraviolet(UV)irradiation,resulting in reduced cooling performance for most polymers,adverse to large-scale practical applications.In this work,we demonstrate a novel polyimide nanofiber(PINF)membrane with a fluorine-containing structure via typical electrospinning technology.The resultant PINF membrane exhibits high sunlight reflectance,UV resistance,and excellent thermal stability,rendering anti-aging day-time radiative cooling.The sunlight reflectance of PINF membranes could maintain constant in the aging test for continuous 720 h under outdoor solar irradiation,exhibiting durable and long-term personal day-time radiative cooling performance.

Cation-πinteractions regulate electrocatalytic water oxidation over iridium single atoms supported on conjugated polymers

Designing cost-effective and high-performing metal catalysts is significant for many renewable energy conversion technologies.Lowering metal loading without sacrificing activity and durability is highly desired for the catalyst design,especially for those reactions where the noble metals deliver the best catalyzing performance.Single-atom catalysts(SACs)with maximal metalatom utilization,homogeneous and tailorable active sites have emerged as promising catalyst candidates,where the local coordination structures of the metal atoms in SACs largely determine the reaction kinetics.Previous design strategies of constructing strong metal-support interactions can stabilize the individual metal atoms in SACs,but present obstacles to provide a flexible manipulation platform for elaborately tailoring the coordination structures to achieve performance optimization towards a specifically targeted reaction.Here,for the proof-of-concept study,we report a novel design of SAC with iridium(Ir)single atoms supported on conjugated polymer,in which the adsorption energies of reaction intermediates on Ir atoms and the reaction kinetics towards acidic water oxidation can be readily optimized through modulating the formed cation-πinteractions that can be tailored by adjusting the molecular structures of conjugated polymers.This strategy establishes a general route to develop targeted SACs for various catalytic reactions.