d-band center engineering of single Cu atom and atomic Ni clusters for enhancing electrochemical CO2 reduction to CO.

The rational design of catalysts with atomic dispersion and a deep understanding of the catalytic mechanism is crucial for achieving high performance in CO2 reduction reaction (CO2RR). Herein, we present an atomically dispersed electrocatalyst with single Cu atom and atomic Ni clusters supported on N-doped mesoporous hollow carbon sphere (CuSANiAC/NMHCS) for highly efficient CO2RR. CuSANiAC/NMHCS demonstrates a remarkable CO Faradaic efficiency (FECO) exceeding 90% across a potential range of -0.6 to -1.2 V vs. reversible hydrogen electrode (RHE) and achieves its peak FECO of 98% at -0.9 V vs. RHE. Theoretical studies reveal that the electron redistribution and modulated electronic structure-notably the positive shift in d-band center of Ni 3d orbital-resulting from the combination of single Cu atom and atomic Ni clusters markedly enhance the CO2 adsorption, facilitate the formation of *COOH intermediate, and thus promote the CO production activity. This study offers fresh perspectives on fabricating atomically dispersed catalysts with superior CO2RR performance.

Heterostructured MnSe/FeSe nanorods encapsulated by carbon with enhanced Na+ diffusion as anode materials for sodium-ion batteries.

The natural abundance of sodium has fostered the development of sodium-ion batteries for large-scale energy storage. However, the low capacity of the anodes hinders their future application. Herein, carbon-encapsulated MnSe-FeSe nanorods (MnSe-FeSe@C) have been fabricated by the in-situ transformation from polydopamine-coated MnO(OH)-Fe2O3. The heterostructure constructed by MnSe and FeSe nanocrystals induces the formation of built-in electric fields, accelerating electron transfer and ion diffusion, thereby improving reaction kinetics. In addition, carbon enclosure can buffer the volumetric stress and enhance the electrical conductivity. These aspects cooperatively endow the anode with superior cycling stability and distinguished rate performance. Specifically, the discharge capacity of MnSe-FeSe@C reaches 414.3 mA h g-1 at 0.1 A g-1 and 388.8 mA h g-1 even at a high current density of 5.0 A g-1. In addition, it still retains a high reversible capacity of 449.2 mA h g-1 after 700 long cycles at 1.0 A g-1. Further, the ab initio calculation has been employed to authenticate the existence of the built-in electric field by Bader charge, indicating that 0.24 electrons in MnSe were transferred to FeSe. The in-situ XRD has been used to evaluate the phase transition during the charging/discharging process, revealing the sodium ion storage mechanism. The construction of heterostructure material paves a new way to design performance-enhanced anode materials for sodium-ion batteries.

Three-dimensional Ni foam supported Pt/NiFe LDH catalyst with enhanced oxygen activation for room-temperature formaldehyde oxidation.

Room-temperature catalytic oxidation of formaldehyde (HCHO) has been extensively investigated due to its high efficiency, convenience, and environmental friendliness. Herein, nickel-iron layered double hydroxide (NiFe LDH) nanosheets were synthesized in-situ on a nickel foil (NF) using a facile one-step hydrothermal method, followed by the deposition of ultra-low content (0.069 wt%) of Pt nanoparticles through NaBH4 reduction. The resulting three-dimensional (3D) hierarchical Pt/NiFe-NF catalyst exhibited exceptional activity for the complete decomposition of formaldehyde to carbon dioxide (CO2) at room temperature (∼95 % conversion within 1 h), as well as remarkable cycling stability. The 3D porous structure of Pt/NiFe-NF provides fast transport channels for the diffusion of gas molecules, making the active catalyst surfaces more accessible. Moreover, abundant hydroxyl groups in NiFe LDH serve as adsorption centers for HCHO molecules to form dioxymethylene (DOM) and formate intermediates. Furthermore, electronic interactions between NiFe LDH and Pt enhance the adsorption and activation of O2 on Pt surfaces, leading to the complete decomposition of intermediates into non-toxic products. This work presents new insights into the design and preparation of Pt-based 3D hierarchical catalysts with surface-rich hydroxyl groups for the efficient removal of indoor HCHO.

Enhancing photocatalytic H2O2 production with Au co-catalysts through electronic structure modification.

Gold-based co-catalysts are a promising class of materials with potential applications in photocatalytic H2O2 production. However, current approaches with Au co-catalysts show limited H2O2 production due to intrinsically weak O2 adsorption at the Au site. We report an approach to strengthen O2 adsorption at Au sites, and to improve H2O2 production, through the formation of electron-deficient Auδ+ sites by modifying the electronic structure. In this case, we report the synthesis of TiO2/MoSx-Au, following selective deposition of Au onto a MoSx surface which is then further anchored onto TiO2. We further show that the catalyst achieves a significantly increased H2O2 production rate of 30.44 mmol g-1 h-1 in O2-saturated solution containing ethanol. Density functional theory calculations and X-ray photoelectron spectroscopy analysis reveal that the MoSx mediator induces the formation of electron-deficient Auδ+ sites thereby decreasing the antibonding-orbital occupancy of Au-Oads and subsequently enhancing O2 adsorption. This strategy may be useful for rationally designing the electronic structure of catalyst surfaces to facilitate artificial photosynthesis.

One-step in-situ construction engineering of ZnO-Zn2SnO4 heterojunction for deeply photocatalytic oxidation of nitric oxide.

The generation of hazardous intermediates during the process of photocatalytic nitric oxide (NO) oxidation presents a tough issue. Herein, a one-step microwave strategy was employed to introduce oxygen vacancies (OVs) into zinc oxide-zinc stannate (ZnO-Zn2SnO4) heterojunction, resulting in an improvement in the photocatalytic efficiency for NO removal. The construction ZnO-Zn2SnO4 heterojunction with the OVs (ZSO-3) owns a significant contribution towards highly efficient electron transfer efficiency (99.7%), which renders ZSO-3 to exert a deep oxidation of NO-to-nitrate (NO3-) rather than NO-to-nitrite (NO2-) or NO-to-nitrogen dioxide (NO2). Based on the solid supports of experimental and simulated calculations, it can be found that OVs play an irreplaceable role in activating small molecules such as NO and O2. Moreover, the enhanced adsorption capacity of small molecules, which guarantees the high yield of active radical due to the formation of S-scheme heterojunction. This work illuminates a novel viewpoint on one-step in-situ route to prepare Zn2SnO4-based heterojunction photocatalyst with deep oxidation ability of NO-to-NO3-.

Facile synthesis of NiCoSe2@carbon anode for high-performance sodium-ion batteries.

Sodium-ion batteries offer significant advantages in terms of low-temperature performance and safety. In this study, we present a straightforward synthetic approach to produce bimetallic selenide NiCoSe2 nanoparticles grown on a three-dimensional porous carbon framework for application as anode materials in sodium-ion batteries. This unique architecture enhances reaction kinetics and structural stability. The three-dimensional interconnected porous carbon network establishes a continuous pathway of electronic conductive, while increasing specific surface area and mitigating volume expansion. Consequently, these features expedite ion transfer and enhance electrolyte interaction. Notably, compared to CoSe, NiCoSe2 exhibits reduced ion transport distances and lower sodium diffusion barriers. Leveraging these attributes, NiCoSe2/N, Se co-doped carbon composite materials (NiCoSe2/NSC) demonstrate a high specific capacity of 320.8 mAh/g, even after 1000 cycles at 5.0 A/g, with a capacity retention rate of 85.1%. The study further delves into the revelation of the reaction mechanism and ion transport pathway through in-situ X-ray diffraction (XRD) analysis and theoretical calculations. The development of these anode materials is poised to pave the way for advancements in sodium-ion battery technology.

Water-Resistance-Based S-Scheme Heterojunction for Deep Mineralization of Toluene.

Deep mineralization of low concentration toluene (C7 H8 ) is one of the most significant but challenging reactions in photocatalysis. It is generally assumed that hydroxyl radicals (⋅OH) as the main reactive species contribute to the enhanced photoactivity, however, it remains ambiguous at this stage. Herein, a S-scheme ZnSn(OH)6 -based heterojunction with AlOOH as water resistant surface layer is in situ designed for tuning the free radical species and achieving deep mineralization of C7 H8 . By employing a combination of in situ DRIFTS and materials characterization techniques, we discover that the dominant intermediates such as benzaldehyde and benzoic acid instead of toxic phenols are formed under the action of holes (h+ ) and superoxide radicals (⋅O2 - ). These dominant intermediates turn out to greatly decrease the ring-opening reaction barrier. This study offers new possibilities for rationally tailoring the active species and thus directionally producing dominant intermediates via designing water resistant surface layer.

Triethanolamine-modified layered double oxide for efficient CO2 capture with low regeneration energy.

Various adsorbents for CO2 capture have been developed to mitigate the greenhouse effect. In this work, a novel CO2 adsorbent was fabricated by depositing triethanolamine (TEOA) onto the surface of nickel-cobalt-aluminum layered double oxide (NiCoAl-LDO) via the impregnation method. The CO2 capacity of the TEOA-LDO composite reached 1.27 mmol/g at 0 °C and 100 kPa, which was twice that of unmodified NiCoAl-LDO. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the hydroxyl groups (-OH) on the surface of NiCoAl-LDO played a significant role in facilitating CO2 adsorption, similar to CO2 adsorption in the presence of H2O, where CO2 is not converted to carbamates but to bicarbonates through base-catalyzed hydration. This bicarbonate pathway doubles the theoretical amine efficiency, increases the CO2 capacity, and reduces the energy consumption during CO2 desorption. The work provides valuable insights into the development of CO2 adsorbents with high capacity, excellent cycling stability, and low regeneration energy.

Construction of 2D S-Scheme Heterojunction Photocatalyst.

Semiconductor photocatalytic technology holds immense promise for converting sustainable solar energy into chemically storable energy, with significant applications in the realms of energy and the environment. However, the inherent issue of rapid recombination of photogenerated electrons and holes hinders the performance of single photocatalysts. To overcome this challenge, the construction of 2D S-scheme heterojunction photocatalysts emerges as an effective strategy. The deliberate design of dimensionality ensures a substantial interfacial area; while, the S-scheme charge transfer mechanism facilitates efficient charge separation and maximizes redox capabilities. This review commences with a fresh perspective on the charge transfer mechanism in S-scheme heterojunctions, followed by a comprehensive exploration of preparation methods and characterization techniques. Subsequently, the recent advancements in 2D S-scheme heterojunction photocatalysts are summarized. Notably, the mechanism behind activity enhancement is elucidated. Finally, the prospects for the development of 2D S-scheme photocatalysts are presented.

Electrochemical and Electrical Biosensors for Wearable and Implantable Electronics Based on Conducting Polymers and Carbon-Based Materials.

Bioelectronic devices are designed to translate biological information into electrical signals and vice versa, thereby bridging the gap between the living biological world and electronic systems. Among different types of bioelectronics devices, wearable and implantable biosensors are particularly important as they offer access to the physiological and biochemical activities of tissues and organs, which is significant in diagnosing and researching various medical conditions. Organic conducting and semiconducting materials, including conducting polymers (CPs) and graphene and carbon nanotubes (CNTs), are some of the most promising candidates for wearable and implantable biosensors. Their unique electrical, electrochemical, and mechanical properties bring new possibilities to bioelectronics that could not be realized by utilizing metals- or silicon-based analogues. The use of organic- and carbon-based conductors in the development of wearable and implantable biosensors has emerged as a rapidly growing research field, with remarkable progress being made in recent years. The use of such materials addresses the issue of mismatched properties between biological tissues and electronic devices, as well as the improvement in the accuracy and fidelity of the transferred information. In this review, we highlight the most recent advances in this field and provide insights into organic and carbon-based (semi)conducting materials' properties and relate these to their applications in wearable/implantable biosensors. We also provide a perspective on the promising potential and exciting future developments of wearable/implantable biosensors.

Plateau pikas near roads are bold and silent when facing a potential predator.

Human disturbance, particularly road traffic, is one of the greatest threats to wildlife. Considering the association between alerting behavior and the survival of animals, it is important to study the effects of road traffic on alerting behavior of wildlife. Previous studies assessing the short-term impact of road traffic on alerting behavior of wildlife have focused on vigilance distances. However, studies on the use of alarm calls are scarce, and it is unclear whether such behavioral responses change after repeated exposure to road traffic. We assessed the alerting behavior of plateau pikas (Ochotona curzoniae) who were near or far from roads when facing a potential predator. We found that pikas near roads exhibited shorter vigilance and tolerance distances, and produced fewer alarm calls than those relatively far away from roads. Furthermore, both vigilance and tolerance distances of plateau pikas were significantly positively correlated with the distance from the burrow to the road. Road traffic reduced antipredator responses and shaped alerting behavior; that is, pikas near roads were bolder and more silent compared to those far away from roads. Our findings suggest that increasing urbanization will have corresponding effects on animal behavior, which may have significant fitness effects in the future.

Modulating the d-Band Center Enables Ultrafine Pt3 Fe Alloy Nanoparticles for pH-Universal Hydrogen Evolution Reaction.

By providing dual active sites to synergistically accelerate H2 O dissociation and H+ reduction, ordered intermetallic alloys usually show extraordinary performance for pH-universal hydrogen evolution reaction (HER). Herein, activated N-doped mesoporous carbon spheres supported intermetallic Pt3 Fe alloys (Pt3 Fe/NMCS-A), as a highly-efficient electrocatalyst for pH-universal HER, are reported. The Pt3 Fe/NMCS-A exhibits low overpotentials (η10 ) of 13, 29, and 48 mV to deliver 10 mA cm-2 in 0.5 m H2 SO4 , 1.0 m KOH, and 1.0 m phosphate buffered solution (PBS), respectively, as well as robust stability to maintain the overall catalytic performances. Theoretical studies reveal that the strong Pt 5d-Fe 3d orbital electronic interactions negatively shift the d-band center (εd ) of Pt 5d orbital, resulting in reduced H* adsorption energy of Pt sites and enhanced acidic HER activity. With Pt and Fe acting as co-adsorption sites for H* and *OH intermediates, respectively, a low energy barrier is required for Pt3 Fe/NMCS-A to dissociate H2 O to afford H* intermediates, which greatly promotes the H* adsorption and H2 formation in alkaline and neutral conditions. The synthetic strategy is further extended to the synthesis of Pt3 Co and Pt3 Ni alloys with excellent HER activity in pH-universal electrolytes, demonstrating the great potential of these Pt-based alloys for practical applications.

Synergistic Effects of Co3Se4 and Ti2C3Tx for Performance Enhancement on Lithium-Sulfur Batteries.

As electronic equipment develops rapidly, higher requirements are placed on electrochemical energy-storage devices. These requirements can be met by a lithium-sulfur (Li-S) battery since it has an impressive energy density of 2600 Wh kg-1 and a high theoretical specific capacity of 1675 mAh g-1. Pitifully, the sluggish redox reaction kinetics and the shuttle effect of polysulfide seriously limit its applications. Separator modification has been proven to be an effective strategy for improving the performance of Li-S batteries. Herein, we have designed a competent three-dimensional separator. It is obtained by embedding Co3Se4 nanoparticles on nitrogen-doped porous carbon (Co3Se4@N-C) by high-temperature selenization of ZIF-67, which are compounded with Ti3C2Tx by electrostatic dispersion self-assembly, and the compound is used to adjust the surface properties of a polypropylene (PP) separator. Due to the synergistic effect of the superior catalytic performance of Co3Se4@N-C and the enhancement of adsorption and conductivity bestowed by Ti3C2Tx, lithium-sulfur batteries perform excellently with the modified PP separator. Specifically, the battery with a Co3Se4@N-C/Ti3C2Tx-modified PP separator exhibits an outstanding rate performance of 787 mAh g-1 at 4C, and stable performance is maintained after 300 cycles at 2C. The density functional theory (DFT) calculations are also performed to confirm the synergistic effect of Co3Se4@N-C and Ti3C2Tx. This design integrates the merits of catalysis and adsorption and provides a new method for constructing high-performance lithium-sulfur batteries.

Single-Atom Engineering of Covalent Organic Framework for Photocatalytic H2 Production Coupled with Benzylamine Oxidation.

In photocatalysis, reducing the exciton binding energy and boosting the conversion of excitons into free charge carriers are vital to enhance photocatalytic activity. This work presents a facile strategy of engineering Pt single atoms on a 2D hydrazone-based covalent organic framework (TCOF) to promote H2 production coupled with selective oxidation of benzylamine. The optimised TCOF-Pt SA photocatalyst with 3 wt% Pt single atom exhibited superior performance to TCOF and TCOF-supported Pt nanoparticle catalysts. The production rates of H2 and N-benzylidenebenzylamine over TCOF-Pt SA3 are 12.6 and 10.9 times higher than those over TCOF, respectively. Empirical characterisation and theoretical simulation showed that the atomically dispersed Pt is stabilised on the TCOF support through the coordinated N1 -Pt-C2 sites, thereby induing the local polarization and improving the dielectric constant to reach the low exciton binding energy. These phenomena led to the promotion of exciton dissociation into electrons and holes and the acceleration of the separation and transport of photoexcited charge carriers from bulk to the surface. This work provides new insights into the regulation of exciton effect for the design of advanced polymer photocatalysts.

Femtosecond transient absorption spectroscopy investigation into the electron transfer mechanism in photocatalysis.

Femtosecond transient absorption spectroscopy (fs-TAS) is a powerful technique for monitoring the electron transfer kinetics in photocatalysis. Several important works have successfully elucidated the electron transfer mechanism in heterojunction photocatalysts (HPs) using fs-TAS measurements, and thus a timely summary of recent advances is essential. This feature article starts with a thorough interpretation of the operating principle of fs-TAS equipment, and the fundamentals of the fs-TAS spectra. Subsequently, the applications of fs-TAS in analyzing the dynamics of photogenerated carriers in semiconductor/metal HPs, semiconductor/carbon HPs, semiconductor/semiconductor HPs, and multicomponent HPs are discussed in sequence. Finally, the significance of fs-TAS in revealing the ultrafast interfacial electron transfer process in HPs is summarized, and further research on the applications of fs-TAS in photocatalysis is proposed. This feature article will provide deep insight into the mechanism of the enhanced photocatalytic performance of HPs from the perspective of electron transfer kinetics.

Verifying the Charge-Transfer Mechanism in S-Scheme Heterojunctions Using Femtosecond Transient Absorption Spectroscopy.

The S-scheme heterojunction is flourishing in photocatalysis because it concurrently realizes separated charge carriers and sufficient redox ability. Steady-state charge transfer has been confirmed by other methods. However, an essential part, the transfer dynamics in S-scheme heterojunctions, is still missing. To compensate, a series of cadmium sulfide/pyrene-alt-difluorinated benzothiadiazole heterojunctions were constructed and the photophysical processes were investigated with femtosecond transient absorption spectroscopy. Encouragingly, an interfacial charge-transfer signal was detected in the spectra of the heterojunction, which provides solid evidence for S-scheme charge transfer to complement the results from well-established methods. Furthermore, the lifetime for interfacial charge transfer was calculated to be ca. 78.6 ps. Moreover, the S-scheme heterojunction photocatalysts exhibit higher photocatalytic conversion of 1,2-diols and H2 production rates than bare cadmium sulfide.

A Portable and Disposable Electrochemical Sensor Utilizing Laser-Scribed Graphene for Rapid SARS-CoV-2 Detection.

The COVID-19 pandemic caused by the virus SARS-CoV-2 was the greatest global threat to human health in the last three years. The most widely used methodologies for the diagnosis of COVID-19 are quantitative reverse transcription polymerase chain reaction (RT-qPCR) and rapid antigen tests (RATs). PCR is time-consuming and requires specialized instrumentation operated by skilled personnel. In contrast, RATs can be used in-home or at point-of-care but are less sensitive, leading to a higher rate of false negative results. In this work, we describe the development of a disposable, electrochemical, and laser-scribed graphene-based biosensor strips for COVID-19 detection that exploits a split-ester bond ligase system (termed 'EsterLigase') for immobilization of a virus-specific nanobody to maintain the out-of-plane orientation of the probe to ensure the efficacy of the probe-target recognition process. An anti-spike VHH E nanobody, genetically fused with the EsterLigase domain, was used as the specific probe for the spike receptor-binding domain (SP-RBD) protein as the target. The recognition between the two was measured by the change in the charge transfer resistance determined by fitting the electrochemical impedance spectroscopy (EIS) spectra. The developed LSG-based biosensor achieved a linear detection range for the SP-RBD from 150 pM to 15 nM with a sensitivity of 0.0866 [log(M)]-1 and a limit of detection (LOD) of 7.68 pM.

A Bifunctional CdS/MoO2 /MoS2 Catalyst Enhances Photocatalytic H2 Evolution and Pyruvic Acid Synthesis.

The best use of photogenerated electrons and holes is crucial to boosting photocatalytic activity. Herein, a bifunctional dual-cocatalyst-modified photocatalyst is constructed based on CdS/MoO2 /MoS2 hollow spheres for hydrogen evolution coupled with selective pyruvic acid (PA) production from lactic acid (LA) oxidation. MoS2 and MoO2 are simultaneously obtained from the conversion of CdMoO4 in one step. In a photocatalytic process, the MoS2 and MoO2 function as the reduction and oxidation centers on which photogenerated electrons and holes accumulate and are used for hydrogen evolution reaction (HER) and PA synthesis, respectively. By monitoring the intermediates, a two-step single-electron route for PA production is proposed, initiated by the cleavage of the α-C(sp3 )-H bond in the LA. The conversion of LA and the selectivity of PA can reach ca. 29 % and 95 % after a five-hour reaction, respectively.

Temperature acclimation in hot-spring snakes and the convergence of cold response.

Animals have evolved sophisticated temperature-sensing systems and mechanisms to detect and respond to ambient temperature changes. As a relict species endemic to the Qinghai-Tibet Plateau, hot-spring snake (Thermophis baileyi) survived the dramatic changes in climate that occurred during plateau uplift and ice ages, providing an excellent opportunity to explore the evolution of temperature sensation in ectotherms. Based on distributional information and behavioral experiments, we found that T. baileyi prefer hot-spring habitats and respond more quickly to warmth than other two snakes, suggesting that T. baileyi may evolve an efficient thermal-sensing system. Using high-quality chromosome-level assembly and comparative genomic analysis, we identified cold acclimation genes experiencing convergent acceleration in high-altitude lineages. We also discovered significant evolutionary changes in thermosensation- and thermoregulation-related genes, including the transient receptor potential (TRP) channels. Among these genes, TRPA1 exhibited three species-specific amino acid replacements, which differed from those found in infrared imaging snakes, implying different temperature-sensing molecular strategies. Based on laser-heating experiments, the T. baileyi-specific mutations in TRPA1 resulted in an increase in heat-induced opening probability and thermal sensitivity of the ion channels under the same degree of temperature stimulation, which may help the organism respond to temperature changes more quickly. These results provide insight into the genetic mechanisms underpinning the evolution of temperature-sensing strategies in ectotherms as well as genetic evidence of temperature acclimation in this group.

Generation of singlet oxygen over CeO2/K,Na-codoped g-C3N4 for tetracycline hydrochloride degradation over a wide pH range.

Singlet oxygen (1O2) species have been widely studied in catalytic oxidation and photodynamic therapy (PDT) and so on due to their unique properties, such as their long lifetime, wide pH tolerance, relative long migration distance, and high selectivity. In this work, 1O2 could be generated over CeO2/K,Na-codoped g-C3N4 heterojunction (CeO2/CN) fabricated using a molten salt method in the presence of H2O2 in dark for the first time, which was used as a Fenton-like catalyst to degrade the emerging tetracycline hydrochloride (TCH) pollutant through a Fenton-like reaction. A significantly-enhanced catalytic activity was observed over CeO2/CN compared with g-C3N4 and commercial CeO2. The Ce4+/Ce3+ redox system was found to play a vital role in the formation of 1O2 from the disproportionation of superoxide radical (˙O2-). The 1O2 and ˙O2- radicals were observed as the main active species in the highly-efficient degradation of TCH over a wide pH range (1.20-11.20). The strong interfacial interaction of CeO2/CN promoted the Ce4+/Ce3+ redox and the generation of active species. The catalytic mechanism of TCH decomposition was also proposed. This finding introduces an efficient and promising approach for the preparation of the highly-effective Fenton-like catalysts for water purification.