Excellent Photothermal Conversion Performance Research Articles

Surface Charge and Nanoparticle Chromophore Coupling to Achieve Fast Exciton Quenching and Efficient Charge Separation in Photoacoustic Imaging (PAI) and Photothermal therapy (PTT)

AbstractAn organic semiconductor nanoparticle (OSN) with surface charge strategy is proposed, which displays excellent photothermal conversion performance. The donor–acceptor hybrid organic semiconductor Y6 is selected as a photothermal chromophore into nanoparticle by self‐assembly, which affords long wavelength absorption, sub‐bandgap emission, and high photon‐to‐thermal conversion. Y6 in OSN adopts closed packing comparing to that in single crystal. The surface charge in OSN causes super‐quenching of the photon excitons, which enhances the nonradiative transition to improve photothermal effect. Lower energy level electronic states are created, which breaks up the bandgap limit and leads to long wavelength emission over 1100 nm. Photothermal therapy and photoacoustic imaging are applied successfully, indicating the success of the new methodology in designing photothermal conversion materials.

Oncocyte Membrane-Camouflaged Multi-Stimuli-Responsive Nanohybrids for Synergistic Amplification of Tumor Oxidative Stresses and Photothermal Enhanced Cancer Therapy

The combination of various therapeutic modalities has received considerable attention for improving antitumor performance. Herein, an innovative nanohybrid, namely CaO2@FePt-DOX@PDA@CM (CFDPM), was developed for synergistic chemotherapy/chemodynamic therapy/Ca2+ overloading-mediated amplification of tumor oxidative stress and photothermal enhanced cancer therapy. Camouflage of the 4T1 cell membrane enabled CFDPM to escape the immune surveillance and accumulate in the tumor tissue. Ca2+, released from CaO2, could lead to mitochondrial dysfunction and facilitate the production of reactive oxygen species to amplify intracellular oxidative stress. Meanwhile, the increase of H2O2 concentration could enhance the efficiency of the chemodynamic therapy (CDT). Moreover, the hypoxic condition could be alleviated remarkably, which is attributed to the sufficient O2 supply by CaO2, resulting in the suppression of drug resistance and promotion of the chemotherapeutic effect. The nanohybrids involving Ca2+ overloading/CDT/chemotherapy could synergistically amplify the tumor oxidative stresses and remarkably aggravate the death of cancer cells. Significantly, the excellent photothermal conversion performance of CFDPM could further promote the tumoricidal effect. The in vitro and in vivo studies revealed that CFDPM could effectively advance the therapeutic efficiency via the cooperation of various therapeutic modalities to optimize their individual virtue, which would open a valuable avenue for effective cancer treatment.

Localized photothermal heating of phosphate-incorporated iron oxide nanosheets enables greatly enhanced water splitting electrocatalysis

Introducing an external energy field into water electrolysis is considered as an innovative strategy to improve electrocatalysis for water splitting. However, rationally modulating these external energy fields to synergize electrocatalytic processes remains a great challenge. Herein, phosphate-incorporated iron oxide nanosheet arrays (P-FeOx/IF) are constructed as multifunctional photothermal-electrocatalytic electrodes for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The as-prepared P-FeOx/IF exhibits excellent photothermal conversion performance and enables in-situ surface self-heating under near-infrared (NIR) light irradiation, resulting in a gradual increase in local temperature on the electrode surface. Impressively, the photothermal P-FeOx/IF electrode exposed to NIR light irradiation shows significantly improved electrocatalytic performances with relatively low overpotentials for OER (η10: 280 mV) and HER (η10: 104 mV) to deliver a current density of 10 mA cm−2. Furthermore, a two-electrode system using photothermal P-FeOx/IF as anode achieves a low cell voltage of 1.685 V. This study provides a new avenue for developing high-performance electrocatalysts incorporating photothermal effects.

TaON doped metal-organic frameworks-based composite phase change materials with excellent photo-thermal conversion performance

It is of great significance for designing prospective composite phase change materials (PCMs) with high shape-stabilized property, good thermal conductivity and efficient energy storage and conversion capacity. This study successfully developed a novel composite PCMs that TaON nanoparticles doped polyethylene glycol/metal-organic frameworks (PEG/MOFs) using a convenient impregnation method. The inherent favorable thermal conductivity of HKUST-1 and the excellent visible light absorption ability of TaON endowed the composite PCMs with remarkably improved thermal conductivity (increased by 126.7% over pure PEG) and remarkable photo-thermal conversion ability (η: 89.9–94.6%). Furthermore, the composite PCMs exhibited not only high shape stability, high thermal energy storage capacity (148.1 J/g) but also outstanding thermal stability and reliability. Accordingly, this novel photothermal composite PCMs would be hopefully applied to efficient storage, management and utilization for solar energy.

Superhydrophobic, biocompatible and durable nanofiber composite with an asymmetric structure for anisotropic strain sensing and body motion detection

Anisotropic strain sensors show multi-directional sensing that can be used to monitor complex human motions. Aligned electrically conductive nanofiber membranes have been candidates for anisotropic strain sensors. Challenges remain for developing nanofiber composite strain sensors with a large workable strain range, corrosion resistance, excellent durability and biocompatibility. Here, we propose a facile vacuum filtration method to prepare an asymmetric nanofiber composite for the anisotropic strain sensing. The carbon nanofibers (CNF)/polydimethylsiloxane (PDMS) are deposited onto an aligned thermoplastic polyurethane (TPU) nanofiber membrane surface, forming a two layered structure. The PDMS ensures strong interfacial adhesion between the TPU nanofibers and the CNF layer, which endows the nanofiber composite with excellent surface stability and durability. The superhydrophobic CNF/PDMS constructs the conductive network, while the aligned nanofiber layer provides the anisotropic mechanical deformation. The nanofiber composite is cytotoxicity-free and exhibits excellent biocompatibility and biosafety. The asymmetric nanofiber composite shows anisotropy in the mechanical property and sensing behavior. The nanofiber composite demonstrates a large working strain range and outstanding sensing durability, and can be used for monitoring the multidirectional body joint motions even under corrosive conditions. Furthermore, the conductive CNF/PDMS exhibits excellent photothermal conversion performance and a negative temperature coefficient (NTC) behavior, and is hence suitable for isotropic temperature sensing. The asymmetric structure opens a new avenue for multifunctional and anisotropic strain sensing.

MXene-based flexible and washable photothermal fabrics for efficiently continuous solar-driven evaporation and desalination of seawater

Solar-driven interface evaporation (SDIE) is a promising seawater desalination technology, which can achieve long-term and efficient seawater desalination in laboratory. However, because of fragile and easily damaged, the solar absorbers are difficult to be applied in the complex and changeable actual applications. In this work, a polypyrrole/Ti3C2Tx MXene-polydopamine-fabric (PPy/MXene-PDA-fabric) was prepared by a simple two-step polymerization method in this study, which can be used as the solar absorber of the SDIE system. Due to the unique physical properties of elastic fabrics, the PPy/MXene-PDA-fabric is easy to transport and clean, making it extremely practical. Meanwhile, the combination of polypyrrole, polydopamine, and MXene photothermal materials also ensures its excellent photothermal conversion performance. The research results show that the average evaporation rate of PPy/MXene-PDA-fabric can reach 1.485 kg/m2h in nearly 100 h of evaporation test under one sun irradiation. After 12 h of continuous operation, only a tiny amount of salt accumulated on the surface of the sample, which could be continued after a simple cleaning. The evaporation rate remained stable after eight cycles. Compared with the traditional solar absorber, PPy/MXene-PDA-fabric not only ensures efficient and durable solar evaporation performance, but also dramatically improves the practicability and environmental applicability.

Multifunctional biomass composite aerogel co-modified by MXene and Ag nanowires for health monitoring and synergistic antibacterial applications

Single function of biomass aerogel restricts its further development, multifunctional biomass aerogel is becoming an urgent need. In this work, multifunctional biomass composite aerogel was prepared by co-modifying MXene and Ag nanowires (AgNWs) on bacterial cellulose/chitosan (BC/CH) composite aerogel through a facile method combining physical mixture, lyophilization and electrostatic adsorption. The as-prepared BC/CH/MXene/AgNWs composite aerogel could be applied as health monitoring sensor and photo-thermal antibacterial material. As a sensor, it showed high sensitivity, short response time, and satisfactory cycling stability for health monitoring. Moreover, the composite aerogel was successfully employed to monitor various human body motions including foot movements, elbow movements, wrist movement, respiration, and throat vibration pronunciation. In addition, the composite aerogel displayed excellent photothermal conversion performance, which could be quickly heated to more than 60 °C in 60 s under NIR laser irradiation (808 nm, 0.6 W/cm2). The BC/CH/MXene/AgNWs composite aerogel showed nearly 100% sterilizing effect due to the synergistic antibacterial effect from common antibacterial role of CH/AgNWs and photo-thermal antibacterial role of MXene. The novel aerogel possesses more response characteristics and better antibacterial property than existing biomass aerogels, which may develop potential application prospect in wearable and implantable bioelectronic material for health monitoring.

Enhanced photothermal conversion capability of melamine foam-derived carbon foam-based form-stable phase change composites

Carbon foams, which can be fabricated from melamine foams via direct carbonization, are promising supporting skeletons for phase change composites due to their excellent light absorption and form-stable features in photothermal conversion and storage. Carbonization temperature and time are two critical parameters during the carbonization process. However, most previous works usually considered the influence of carbonization temperature or time. As an improvement, this work simultaneously studies the impacts of carbonization temperature and time on the hypothesis of their synergetic effects on the mechanical, thermal, and optical properties of the melamine foam-derived carbon foams, aiming to determine the optimal carbonization process. The results indicated a critical carbonization temperature of approximately 350 °C, below which melamine foams could be partially carbonized even by extending the carbonization time to 180 min, leading to the low light absorption capability. Once exceeding 350 °C, the absorbance of the synthesized carbon foams in the solar spectrum was improved by more than 12.6%, mainly due to the super conjugated π bonds and C–C bonds formed within the carbon foams. With a further increase in the carbonization temperature, the charging efficiency of the phase change composite was slightly increased by 1.7%, but the mechanical strength of the carbon foams was declined by 38.4%. Besides, carbonization time presented a negligible effect on the charging efficiency. The optimal carbonization temperature and time were determined to be 350 °C and 5 min, respectively, and the corresponding charging and discharging efficiencies were 90.1% and 90.7%, demonstrating the excellent photothermal conversion performance of the proposed carbon foam-based phase change composites.

Black phosphorus-incorporated titanium dioxide nanotube arrays for near-infrared–triggered drug delivery

Inflammatory reaction after implantation is a serve complication of medical implants. Here, we propose a near-infrared (NIR) light stimulus-responsive drug-eluting platform based on titanium dioxide nanotube (TNT) arrays. Nano-sized black phosphorus (BP) prepared using a liquid exfoliation method served as a photothermal agent and were incorporated with TNTs, imparting TNTs NIR stimulus-responsive activity. The combination of BP and TNTs exhibited excellent photothermal conversion performance. Ibuprofen, a commonly used anti-inflammatory drug, was selected as the model drug and loaded on the NIR-responsive functional TNTs. A coating of 1-tetradecanol (TD) was used as a thermosensitive gatekeeper to prevent drug release at normal body temperature. Upon exposure to NIR light, the NIR-responsive drug delivery system transformed light energy to thermal energy that melted the TD layer and led to drug release from the reservoir. Furthermore, the combination of BP and TNTs showed enhanced biomineralization performance because of the degradation of BP into phosphate. Moreover, BP-modified TNTs showed no obvious cytotoxicity to MC3T3-E1 cells. Thus, this NIR light-responsive drug delivery system shows potential for controlled drug delivery in Ti-based orthopedic implants to overcome the challenges of tissue inflammation after implantation.

Chitosan assisted MXene decoration onto polymer fabric for high efficiency solar driven interfacial evaporation of oil contaminated seawater

The solar-driven interfacial evaporation (SDIE) is now a promising way to solve the shortage of fresh water. However, high performance SDIE for the oil contaminated seawater remains challenging. Here, we propose a facile “chitosan assisted MXene decoration” strategy to prepare a superhydrophilic and underwater superoleophobic Chitosan/MXene/fabric (CMF) for highly efficient SDIE. Benefiting from the superhydrophilicity and excellent photo-thermal conversion performance, the CMF is served as both the solar absorber and the water transportation path. Under the light illumination with one sun intensity (1 kW·m−2), a high evaporation rate of 1.50 kg·m−2·h−1 and efficiency of 88.05% are achieved. The strong interfacial interaction and outstanding salt rejection behavior of the CMF ensure the SDIE long-term stability and durability. In addition, the underwater superoleophobic CMF can effectively and quickly repel different oils and is hence suitable for high performance SDIE of the oil-in-water emulsion and the crude oil contaminated seawater. This work provides a rational design and optimization for the SDIE system, which holds great potential in practical desalination applications.

Electron Transfer Strategies to Regulate Carriers' Separation for Intensive Pyroelectric Dynamic Therapy With Simultaneous Photothermal Therapy.

Endogenic heat shock proteins and uneven local heat distribution are two main problems in traditional tumor hyperthermia therapy strategies. Aiming at solving these problems, we designed Au–SnSe–PVP nanomaterials (ASNPs) by modifying Au nanoparticles (Au-NPs) and biocompatible PVP on SnSe nanorods via a new reactive oxygen species production strategy. The ASNPs with excellent photothermal conversion performance can produce thermoelectric effects in response to temperature differences during photothermal conversion. The modification of Au-NPs can attract free electron (e–) to accumulate and promote the separation of e– and holes (h+) in the thermoelectric process, thereby further promoting e–-rich Au-NPs-induced H2O2 homolysis and h+–H2O half-reaction to generate hydroxyl radicals, realizing the synergistic application of photothermal therapy and pyroelectric dynamic therapy in tumor treatment.

Scalable carbon black deposited fabric/hydrogel composites for affordable solar-driven water purification

l. Bilayer fabric/hydrogel composites exhibit tough interfacial bonding. 2. The hydrogel substrate combines high mechanical strength and water absorption. 3. The composites function well as effective interfacial evaporator for water purification. Interfacial solar-driven evaporators have presented great potential for water purification owing to their low energy consumption and high steam generation efficiency. However, their further applications are hindered by the high costs and complicated fabrication processes. Here, a scalable bilayer interfacial evaporator was constructed via an affordable technique, in which carbon black deposited nonwoven fabric (CB@NF) was employed as the upper photothermal layer, as well as PVA/starch hybrid hydrogel for self-floating and water transport. Under simulated one sun irradiation, CB@NF layer displayed excellent photothermal conversion performance, whose temperature could increase 30.4 °C within 15 min. Moreover, the introduction of starch into PVA endowed the hybrid hydrogels with considerable water-absorption capability on the premise of ensuring mechanical properties. The resultant CB@NF/PVA/starch composites achieved superior interfacial adhesion performance with interfacial toughness at about 200 J m −2 . Combining with good evaporation performance, salt-rejection property and high purification efficiency on pollutants, this evaporation system would become a promising candidate to alleviate water shortage.

Acid-Sensitive Nanoparticles Based on Molybdenum Disulfide for Photothermal-Chemo Therapy.

The combination of multiple treatments has recently been investigated for tumor treatment. In this study, molybdenum disulfide (MoS2) with excellent photothermal conversion performance was used as the core, and manganese dioxide (MnO2), which responds to the tumor microenvironment, was loaded on its surface by liquid deposition to form a mesoporous core-shell structure. Then, the chemotherapeutic drug Adriamycin (DOX) was loaded into the hole. To further enhance its water solubility and stability, the surface of MnO2 was modified with mPEG-NH2 to prepare the combined antitumor nanocomposite MoS2@DOX/MnO2-PEG (MDMP). The results showed that MDMP had a diameter of about 236 nm, its photothermal conversion efficiency was 33.7%, and the loading and release rates of DOX were 13 and 65%, respectively. During in vivo and in vitro studies, MDMP showed excellent antitumor activity. Under the combined treatment, the tumor cell viability rate was only 11.8%. This nanocomposite exhibits considerable potential for chemo-photothermal combined antitumor therapy.

Synthesis and characterization of hydroxylated carbon nanotubes modified microencapsulated phase change materials with high latent heat and thermal conductivity for solar energy storage

The excellent thermal storage and photothermal conversion performance are of significance for the microencapsulated phase change materials (MicroPCMs) in solar energy storage applications. Herein, the hydroxylated carbon nanotubes (HO-CNTs) modified MicroPCMs with n-hexadecanol core and melamine-formaldehyde (MF) resin shell were successfully fabricated via in-situ polymerization, where the effect of dosing amounts of HO-CNTs on the thermal properties of MicroPCMs was investigated. The micromorphology shows that the introduction of HO-CNTs has little influence on the spherical structure of MicroPCMs with compact shell. At the 0.2 wt% dosage of HO-CNTs, the melting temperature and latent heat of MicroPCMs are 51.5 °C and 181.5 J g −1 , respectively, and the energy storage efficiency of n-hexadecanol is calculated to be 75.25%. It is noteworthy that with the increase of HO-CNTs dosage, the prepared MicroPCMs exhibit prominent improvement in the thermal conductivity and photothermal conversion performance, being conducive to enhancing photothermal storage efficiency. The thermal conductivity of MicroPCMs is as high as 0.3598 W m −1 K −1 with the dosing amount of 0.6 wt% HO-CNTs. Additionally, all the modified MicroPCMs possess distinguished thermal reliability during the 500 thermal cycles. The results suggest that the developed MicroPCMs with high thermal storage capacity and excellent photothermal conversion performance have a great potential application in the direct absorption solar collector system (DASC) for solar energy storage. • The core-shell MicroPCMs modified by HO-CNTs were fabricated via in-situ polymerization. • The latent heat of modified McroPCMs is as high as 181.5 J g −1 with the content of 0.2 wt% HO-CNTs. • The modified MicroPCMs obtain a significant enhancement in thermal conductivity and photothermal conversion performance. • The as-prepared MicroPCMs possess excellent thermal reliability during the 500 phase change cycles.

Inside Back Cover: Kinetics‐Regulated Interfacial Selective Superassembly of Asymmetric Smart Nanovehicles with Tailored Topological Hollow Architectures (Angew. Chem. Int. Ed. 12/2022)

A kinetics-regulated cooperative polymerization induced interfacial superassembly strategy is used by Biao Kong and co-workers in their Research Article (e202200240) to construct a series of asymmetric hollow porous composites with tunable diameters, architectures, and compositions. Owing to their excellent photothermal conversion performance and unique nanostructures, the resulting nanoparticles can be utilized as NIR light triggered nanovehicles with controllable cargo release.

Kinetics‐Regulated Interfacial Selective Superassembly of Asymmetric Smart Nanovehicles with Tailored Topological Hollow Architectures

AbstractHollow nanoparticles featuring tunable structures with spatial and chemical specificity are of fundamental interest. However, it remains a significant challenge to design and synthesize asymmetric nanoparticles with controllable topological hollow architecture. Here, a versatile kinetics‐regulated cooperative polymerization induced interfacial selective superassembly strategy is demonstrated to construct a series of asymmetric hollow porous composites (AHPCs) with tunable diameters, architectures and components. The size and number of patches on Janus nanoparticles can be precisely manipulated by the precursor and catalyst content. Notably, AHPCs exhibit excellent photothermal conversion performance under the irradiation of a near infrared (NIR) laser. Thus, AHPCs are utilized as NIR light‐triggered nanovehicles and cargos can be controllably released. In brief, this versatile superassembly approach offers a streamlined and powerful toolset to design diverse asymmetric hollow porous composites.

Kinetics-Regulated Interfacial Selective Superassembly of Asymmetric Smart Nanovehicles with Tailored Topological Hollow Architectures.

Hollow nanoparticles featuring tunable structures with spatial and chemical specificity are of fundamental interest. However, it remains a significant challenge to design and synthesize asymmetric nanoparticles with controllable topological hollow architecture. Here, a versatile kinetics-regulated cooperative polymerization induced interfacial selective superassembly strategy is demonstrated to construct a series of asymmetric hollow porous composites (AHPCs) with tunable diameters, architectures and components. The size and number of patches on Janus nanoparticles can be precisely manipulated by the precursor and catalyst content. Notably, AHPCs exhibit excellent photothermal conversion performance under the irradiation of a near infrared (NIR) laser. Thus, AHPCs are utilized as NIR light-triggered nanovehicles and cargos can be controllably released. In brief, this versatile superassembly approach offers a streamlined and powerful toolset to design diverse asymmetric hollow porous composites.

Photothermal trap with multi-scale micro-nano hierarchical structure enhances light absorption and promote photothermal anti-icing/deicing

Facing climate change caused by carbon emissions and the disaster of ice accumulation on outdoor equipment, the large-scale use of solar energy is a promising solution. Here, a photothermal anti-icing material composed of substrate, carbon-based light-absorption layer, and encapsulation layer was prepared using a combined template-spraying method. The multi-scale micro-nano hierarchical structure can enhance light absorption in a limited space due to the light trapping effect, which was confirmed by ray-tracing simulation and the UV–vis-NIR light absorption result, and the average light absorption rate is up to ∼ 98% at the 200–2000 nm wavelength. The average surface temperature can reach ∼ 85 °C under 1 sun (qi = 100 mW/cm2) illumination at room temperature (Tr = 25 °C), and the photo-to-thermal conversion efficiency is up to 60.76%. Excellent photothermal conversion performance endows the material with the ability of photothermal deicing, and the frost or ice layer can melt and fall off from the surface after 300 s of 1 sun illumination. Besides, the photothermal anti-icing experiments under 1 sun illumination show that the prepared material has a lower freezing temperature (-25.20 ± 1.34 °C), a longer freezing delay time (774.76 ± 114.19 s), and a heat transfer model during the icing process was proposed. Surface friction, water flow impact, and solution immersion tests show that the material has excellent mechanical durability and chemical stability. The materials prepared in this work show enormous application potential on outdoor equipment due to the simple preparation method, strong mechanical durability, and excellent photothermal anti-icing/deicing properties.

Self-floating Ti3C2 MXene-coated polyurethane sponge with excellent photothermal conversion performance for peroxydisulfate activation and clean water production

• MXene@PU photothermal conversion module reached 140 °C interfacial temperature. • Thermal activation of PDS significantly enhanced the degradation of organic pollutants. • Abundant recycled water was produced in photothermal conversion process. The self-floating Ti 3 C 2 MXene-coated polyurethane sponge (MXene@PU module) was prepared via the simple coating operation for thermal activation of peroxydisulfate (PDS) and production of clean water. Coating MXene on the surface of PU significantly improved the degradation of model pollutant carbamazepine (CBZ) compared with PU alone under simulated solar radiation. Because of the excellent photothermal conversion performance of Ti 3 C 2 MXene and the unique double-deck structure of MXene@PU module, the interfacial temperature of MXene@PU module reached about 140 °C, far higher than that of PU (about 82 °C). Radical identification experiments demonstrated that both hydroxyl radical and sulfate radical contributed to the degradation of organic pollutant. Addition of Cl − , HPO 4 2− , HCO 3 − and natural organic matter in solution generated inhibitory effect on CBZ degradation. The prepared MXene@PU module exhibited excellent stability after long-time experiment. Importantly, the interfacial evaporation process produced abundant recycled water and no pollutant was detected in recycled water. This study provides a feasible way to utilize the renewable solar energy for removal of organic pollutants and production of clean water.

Superhydrophobic light-driven actuator based on self-densified wood film with a sandwich-like structure

Response actuators based on different stimuli such as light, humidity and temperature have attracted extensive attention due to their advantages in various environments. In this work, a facile top-down strategy is proposed to prepare a light stimuli-responsive self-densified wood film. We constructed a sandwich-like structure by in-situ co-precipitation of Fe3O4, spraying CNT, self-densification and chemical vapor deposition methyltrimethoxysilane (MTMS) on TEMPO-oxidized delignified wood. The CNT/Fe3O4/MTMS wood film exhibits excellent strength (56 Mpa along the fiber direction), superhydrophobicity (water contact angle of 151°) and photothermal conversion performance. The Fe3O4 in the film plays a good role of photothermal conversion, which makes the photothermal conversion effect of the film double that of the wood film sprayed only with CNT. Under near-infrared (NIR) light irradiation and focused sunlight, the film exhibits a light-driven response of linear motion on the water surface. Based on the excellent electrical conductivity and light stimulus responsiveness of the film under NIR irradiation, an electrical switch is successfully designed and can be remotely controlled. Moreover, the film is easy to recycle due to magnetism, it is also very stable under moisture environment due to the protection of the superhydrophobic coating and the dense structure created by self-densification.