Operando Spectroscopic Elucidation of the Bubble Sunshade Effect in Inorganic-Biological Hybrids for Photosynthetic Hydrogen Production.

Hydrogen production by photosynthetic hybrid systems (PBSs) offers a promising avenue for renewable energy. However, the light-harvesting efficiency of PBSs remains constrained due to unclear intracellular kinetic factors. Here, we present an operando elucidation of the sluggish light-harvesting behavior for existing PBSs and strategies to circumvent them. By quantifying the spectral shift in the structural color scattering of individual PBSs during the photosynthetic process, we observe the accumulation of product hydrogen bubbles on their outer membrane. These bubbles act as a sunshade and inhibit light absorption. This phenomenon elucidates the intrinsic constraints on the light-harvesting efficiency of PBSs. The introduction of a tension eliminator into the PBSs effectively improves the bubble sunshade effect and results in a 4.5-fold increase in the light-harvesting efficiency. This work provides valuable insights into the dynamics of transmembrane transport gas products and holds the potential to inspire innovative designs for improving the light-harvesting efficiency of PBSs.

Anisotropic growth of gold anchors on CdSe semiconductor quantum platelets for self-assembled architectures with well-connected electronic circuits for the electrochemical detection of enrofloxacin.

Anisotropic growth of nanomaterials enables advances in building diverse and complex architectures, which exhibit unique properties and enrich the choice of nano-building modules for electrochemical sensor devices. Herein, an anisotropic growth method was proposed to anchor gold nanoparticles (AuNPs) onto both ends of quasi-two-dimensional CdSe semiconductor quantum nanoplatelets (NPLs), appearing with a monodisperse and uniform nano-dumbbell shape. Then, these AuNPs were exploited as natural anchor points and further initiated self-assembly to create complex architectures via dithiol bridges. Detailed studies illustrated that the covalent Se-Au bonds facilitate effective charge transfer in the internal metal-semiconductor (M-S) electric field. The narrowed energy gap and up-shifted highest occupied molecular orbital were favored for electron removal during the electro-oxidation process. The ultrathin CdSe NPLs supplied a large specific surface area, carrying remaining holes and abundant active sites for target electro-catalysis. As a result, using the assembled complex as the electrode matrix with well-connected electronic circuits, a reliable electrochemical sensor was achieved for enrofloxacin detection. Under the optimal conditions, the current response exhibits two linear dynamic ranges, 0.01-10.0 µM and 10.0-250 µM, and the detection limit was calculated as 0.0026 µM. This work not only opens up broad application prospects for heterogeneous M-S combinations as effective electrochemical matrixes but also develops reliable antibiotic assays for food and environmental safety.

Cu-based catalyst designs in CO2 electroreduction: precise modulation of reaction intermediates for high-value chemical generation.

The massive emission of excess greenhouse gases (mainly CO2) have an irreversible impact on the Earth's ecology. Electrocatalytic CO2 reduction (ECR), a technique that utilizes renewable energy sources to create highly reduced chemicals (e.g. C2H4, C2H5OH), has attracted significant attention in the science community. Cu-based catalysts have emerged as promising candidates for ECR, particularly in producing multi-carbon products that hold substantial value in modern industries. The formation of multi-carbon products involves a range of transient intermediates, the behaviour of which critically influences the reaction pathway and product distribution. Consequently, achieving desirable products necessitates precise regulation of these intermediates. This review explores state-of-the-art designs of Cu-based catalysts, classified into three categories based on the different prospects of the intermediates' modulation: heteroatom doping, morphological structure engineering, and local catalytic environment engineering. These catalyst designs enable efficient multi-carbon generation in ECR by effectively modulating reaction intermediates.

Photocatalytic Conversion of Methane: Current State of the Art, Challenges, and Future Perspectives.

With 28-34 times the greenhouse effect of CO2 over a 100-year period, methane is regarded as the second largest contributor to global warming. Reducing methane emissions is a necessary measure to limit global warming to below 1.5 °C. Photocatalytic conversion of methane is a promising approach to alleviate the atmospheric methane concentrations due to its low energy consumption and environmentally friendly characteristics. Meanwhile, this conversion process can produce valuable chemicals and liquid fuels such as CH3OH, CH3CH2OH, C2H6, and C2H4, cutting down the dependence of chemical production on crude oil. However, the development of photocatalysts with a high methane conversion efficiency and product selectivity remains challenging. In this review, we overview recent advances in semiconductor-based photocatalysts for methane conversion and present catalyst design strategies, including morphology control, heteroatom doping, facet engineering, and cocatalysts modification. To gain a comprehensive understanding of photocatalytic methane conversion, the conversion pathways and mechanisms in these systems are analyzed in detail. Moreover, the role of electron scavengers in methane conversion performance is briefly discussed. Subsequently, we summarize the anthropogenic methane emission scenarios on earth and discuss the application potential of photocatalytic methane conversion. Finally, challenges and future directions for photocatalytic methane conversion are presented.

Synergistic treatment of carbon dioxide and nitrogen-containing wastewater by electrochemical C-N coupling.

Electrocatalytic CO2 reduction technology has been considered a promising approach to alleviate the severe environmental and energy issues caused by the anthropogenic over-emission of CO2. Coupling CO2 reduction with nitrogen (N)-pollutants reduction from wastewater to produce higher valued products (e.g., urea, amide, amine, etc.) could significantly extend the application scenarios and product categories of CO2 reduction technologies. This paper investigates the available CO2 and N-pollutants sources and summarizes the recent progress of electrocatalytic C-N coupling reactions. Based on the fundamental research, technical concerns for scale-up applications of C-N coupling electrocatalysis are thoroughly discussed. Finally, we prospect the opportunities and challenges with an in-depth understanding of the underlying dominant factors in applying C-N coupling electrocatalysis. Further development in recycling CO2 and N pollutants via the electrocatalytic C-N coupling process is also discussed.

Enriching Reaction Intermediates in Multishell Structured Copper Catalysts for Boosted Propanol Electrosynthesis from Carbon Monoxide.

Fine-tuned catalysts that alter the diffusion kinetics of reaction intermediates is of great importance for achieving high-performance multicarbon (C2+) product generation in carbon monoxide (CO) reduction. Herein, we conduct a structural design based on Cu2O nanoparticles and present an effective strategy for enhancing propanol electrosynthesis from CO. The electrochemical characterization, operando Raman monitoring, and finite-element method simulations reveal that the multishell structured catalyst can realize the enrichment of C1 and C2 intermediates by nanoconfinement space, leading to the possibility of further coupling. Consequently, the multishell copper catalyst realizes a high Faraday efficiency of 22.22 ± 0.38% toward propanol at the current density of 50 mA cm-2.

Accelerating ammonia synthesis in a membraneless flow electrolyzer through coupling ambient dinitrogen oxidation and water splitting.

An electrochemical approach for ammonia production is successfully developed by coupling the anodic dinitrogen oxidation reaction (NOR) and cathodic hydrogen evolution reaction (HER) within a well-designed membraneless flow electrolyzer. The obtained reactor shows the preferential yield of ammonia over nitrogen oxides on the vanadium nitride catalyst surface. At an applied oxidation potential of 2.25 V versus the reversible hydrogen electrode (vs RHE), a promoted ammonia production rate and Faradaic efficiency (FE) were obtained with 9.9 mmol g-1 h-1 (0.029 mmol cm-2 h-1) and 4.8%, respectively. Besides, the negative affection of ammonia contamination is efficiently alleviated. Density functional theory calculations revealed that the thermodynamic energy needed to produce ammonia (-0.63 eV) is far lower than that of producing nitrogen oxide (0.96 eV) from hydrogenated nitrogen oxides [∗N2OH] splitting, confirming the coupling of NOR and HER.

Miniaturized Microfluidic Electrochemical Biosensors Powered by Enzymatic Biofuel Cell.

Electrochemical biosensors, in which enzymatic biofuel cells simultaneously work as energy power and signal generators, have become a research hotspot. They display the merits of power self-support, a simplified structure, in vivo operational feasibility, online and timely monitoring, etc. Since the concept of enzymatic biofuel cell-powered biosensors (EBFC-SPBs) was first proposed, its applications in health monitoring have scored tremendous achievements. However, the creation and practical application of portable EBFC-SPBs are still impeded by the difficulty in their miniaturization. In recent years, the booming microfluidic technology has powerfully pushed forward the progress made in miniaturized and portable EBFC-SPBs. This brief review recalls and summarizes the achievements and progress made in miniaturized EBFC-SPBs. In addition, we also discuss the advantages and challenges that microfluidic and screen-printing technologies provide to wearable and disposable EBFC-SPBs.

Two-Dimensional Fe-N-C Single-Atomic-Site Catalysts with Boosted Peroxidase-Like Activity for a Sensitive Immunoassay.

Single-atomic-site catalysts (SASCs) with peroxidase (POD)-like activities have been widely used in various sensing platforms, like the enzyme-linked immunosorbent assay (ELISA). Herein, a two-dimensional Fe-N-C-based SASC (2D Fe-SASC) is successfully synthesized with excellent POD-like activity (specific activity = 90.11 U/mg) and is used to design the ELISA for herbicide detection. The 2D structure of Fe-SASC enables the exposure of numerous single atomic active sites on the surface as well as boosts the POD-like activity, thereby enhancing the sensing performance. 2D Fe-SASC is assembled into competitive ELISA kit, which achieves an excellent detection performance for 2,4-dichlorophenoxyacetic acid (2,4-D). Fe-SASC has great potential in replacing high-cost natural enzymes and working on various advanced sensing platforms with high sensitivity for the detection of various target biomarkers.

Singlet oxygen generation in light-assisted peroxymonosulfate activation by carbon nitride: Role of elevated crystallinity.

Carbon nitride (CN) is an emerging 2D non-metal semiconductor material that could be used in photocatalysis and advanced oxidation processes (AOPs) for pollutants degradation. The radical-induced degradation by CN in photocatalysis or photo-assisted AOPs was widely reported in previous studies. Nevertheless, how the non-radical degradation by CN materials could be achieved under irradiation is neither well understood nor controlled. In this work, crystalline carbon nitride (CCN) was synthesized via a facile molten-salt method, and used to activate peroxymonosulfate (PMS) under visible light (>420 nm) to selectively and efficiently degrade tetracycline (TC). Compared to the traditional polymeric carbon nitride (PCN), CCN was found to be a superior PMS activator with the assistance of visible light, which was ascribed to the increased crystallinity of CN tri-s-triazine units and the increased number of catalytic sites, thereby optimizing the photoelectric properties. The activation performance could be further improved by copper loading, with TC degradation rate nearly six times more than that of PCN. EPR trapping and quenching tests showed that singlet oxygen (1O2) was the dominant reactive oxygen species in the CCN/PMS/visible light system, attributing to the increased graphitic N sites and formation of electron-deficient C in C-N bonding between neighboring tri-s-triazine units upon crystallinity elevation in CCN. In contrast to the conventional radical-based photocatalysis and AOP processes, the visible light-assisted non-radical AOP degradation was highlighted for the selectivity and the remarkable resistance to the impacts of background inorganic anions or natural organic matter (up to 10 mg/L) in the actual water matrix. This work revealed the 1O2 generation mechanism by CN-based materials under the joint assistance of visible light illumination and crystallinity elevation, and its excellent removal performance demonstrates the great potential of CCN-based materials in the practical wastewater treatment.

Optimization of integrated anaerobic digestion and pyrolysis for biogas, biochar and bio-oil production from the perspective of energy flow.

Valorization of lignocellulosic biomass via anaerobic digestion (AD) is limited by its reluctant structure, leading to a substantial energy remaining in the solid digestate. To mitigate this effect, the integration of AD and pyrolysis has attracted attention in recent years. However, the energy recovery efficiency of this cascading system is still unclear, especially the time node. Herein, a comprehensive evaluation of this integration, using varied AD periods, was conducted, to produce biogas, bio-oil and biochar, and to enhance the energy recovery, from the perspective of energy flow. The result indicated that the accumulative CH4 yields increased from 33.23 to 249.20 mL/g VS as the AD time increased from 3 to 15 days. Pyrolysis of the obtained solid digestate obtained biochar from 28.81 to 35.96 %, while the bio-oil and pyrolysis gas slowly decreased. The highest energy efficiency of 71.9 % with a net energy gain of 2.0 MJ/kg wet biomass was achieved by the coupled system optimization at an AD time of 12 days as suggested by the energy flow analysis. This study provides new insight for the maximal conversion of biomass waste into energy products and provides a new way of recycling it.

Supramolecular assemblies of a newly developed indole derivative for selective adsorption and photo-destruction of perfluoroalkyl substances.

Per-/polyfluoroalkyl substances (PFASs) contamination has caused worldwide health concerns, and increased demand for effective elimination strategies. Herein, we developed a new indole derivative decorated with a hexadecane chain and a tertiary amine center (named di-indole hexadecyl ammonium, DIHA), which can form stable nanospheres (100-200 nm) in water via supramolecular assembly. As the DIHA nanospheres can induce electrostatic, hydrophobic and van der Waals interactions (all are long-ranged) that operative cooperatively, in addition to the nano-sized particles with large surface area, the DIHA nanocomposite exhibited extremely fast adsorption rates (in seconds), high adsorption capacities (0.764-0.857 g g-1) and selective adsorption for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), outperformed the previous reported high-end PFASs adsorbents. Simultaneously, the DIHA nanospheres can produce hydrated electron (eaq-) when subjected to UV irradiation, with the virtue of constraining the photo-generated eaq- and the adsorbed PFOA/PFOS molecules entirely inside the nanocomposite. As such, the UV/DIHA system exhibits extremely high degradation/defluorination efficiency for PFOA/PFOS, even under ambient conditions, especially with the advantages of low chemical dosage requirement (µM level) and robust performance against environmental variables. Therefore, it is a new attempt of using supramolecular approach to construct an indole-based nanocomposite, which can elegantly combine adsorption and degradation functions. The novel DIHA nanoemulsion system would shed light on the treatment of PFAS-contaminated wastewater.

Hierarchical S-modified Cu porous nanoflakes for efficient CO2 electroreduction to formate.

Electrochemical reduction of CO2 into liquid fuels is a promising approach to achieving a carbon-neutral energy cycle but remains a great challenge due to the lack of efficient catalysts. Here, the hierarchical architectures assembled by ultrathin and porous S-modified Cu nanoflakes (Cu-S NFs) are designed and constructed as an efficient electrocatalyst for CO2 conversion to formate with high partial current density. Specifically, when integrated into a gas diffusion electrode in a flow cell, Cu-S NFs are capable of delivering the ultrahigh formate current density up to 404.1 mA cm-2 with a selectivity of 89.8%. Electrochemical tests and theoretical calculations indicate that the superior performance of the designed catalysts may be attributed to the unique structure, which can provide abundant active sites, fast charge transfer, and highly active edge sites.

Single-Atomic Iron Doped Carbon Dots with Both Photoluminescence and Oxidase-Like Activity.

Multifunctional nanozymes can benefit biochemical analysis via expanding sensing modes and enhancing analytical performance, but designing multifunctional nanozymes to realize the desired sensing of targets is challenging. In this work, single-atomic iron doped carbon dots (SA Fe-CDs) are designed and synthesized via a facile in situ pyrolysis process. The small-sized CDs not only maintain their tunable fluorescence, but also serve as a support for loading dispersed active sites. Monoatomic Fe offers SA Fe-CDs exceptional oxidase-mimetic activity to catalyze 3,3',5,5'-tetramethylbenzidine (TMB) oxidation with fast response (Vmax  = 10.4 nM s-1 ) and strong affinity (Km  = 168 µM). Meanwhile, their photoluminescence is quenched by the oxidation product of TMB due to inner filter effect. Phosphate ions (Pi) can suppress the oxidase-mimicking activity and restore the photoluminescence of SA Fe-CDs by interacting with Fe active sites. Based on this principle, a dual-mode colorimetric and fluorescence assay of Pi with high sensitivity, selectivity, and rapid response is established. This work paves a path to develop multifunctional enzyme-like catalysts, and offers a simple but efficient dual-mode method for phosphate monitoring, which will inspire the exploration of multi-mode sensing strategies based on nanozyme catalysis.

2D Catalysts for CO2 Photoreduction: Discussing Structure Efficiency Strategies and Prospects for Scaled Production Based on Current Progress.

Currently, the excessive consumption of fossil fuels is accompanied by massive emissions of CO2 , leading to severe energy shortages and intensified global warming. It is of great significance to develop and use renewable clean energy while reducing the concentration of CO2 in the atmosphere. Photocatalytic technology is a promising strategy for carbon dioxide conversion. Clearly, the achievement of the above goals largely depends on the design and construction of catalysts. This review is mainly focused on the application of 2D materials for photocatalytic CO2 reduction. The contribution of synthetic strategies to their structure and performance is emphasized. Finally, the current challenges, and prospects of 2D materials for photoreduction of CO2 with high efficiency, even for practical applications are discussed. It is hoped that this review can provide some guidance for the rational design, controllable synthesis of 2D materials, and their application for efficient photocatalytic CO2 reduction.

In situ formed N-containing copper nanoparticles: a high-performance catalyst toward carbon monoxide electroreduction to multicarbon products with high faradaic efficiency and current density.

Developing efficient catalysts for electrochemical carbon monoxide reduction (ECOR) with high faradaic efficiency (FE) and current density is highly desirable. In this work, we demonstrate that the N-containing Cu nanoparticles formed in situ by the reconstruction of cuprous 7,7,8,8-tetracyanoquinodimethane possess high-performance ECOR ability. Impressively, the N-containing Cu nanoparticle catalyst presented the highest FE of 81.31% towards multicarbon products with a high commercial-grade partial current density of 162.62 mA cm-2, which is among the best of the reported Cu-based ECOR catalysts at -0.69 V versus the reversible hydrogen electrode. The retained ligand on the formed catalyst via the convenient in situ formation is crucial for the selectivity of multicarbon products. This work will arouse enthusiasm for the utilization of reconstruction features for designing ligand-containing catalysts with enhanced artificial carbon fixation ability.

An Iron(III)-Based Metal-Organic Gel-Catalyzed Dual Electrochemiluminescence System for Cytosensing and In Situ Evaluation of the VEGF165 Subtype.

The recent surge of interest in metal-organic gels (MOGs) has emerged for their soft porous structure, large surface area, and abundant active metal sites, making them a promising candidate for building catalyst matrices. In this work, facilely synthesized Fe(III)-organic gel was directly used as a robust electrode matrix. Detailed studies illustrated that their Fe(III) centers can speed up the electro-oxidation/reduction of the H2O2 coreactant to produce reactive oxygen species for enhancing a potential-resolved dual electrochemiluminescence (ECL) emission. Among them, the anodic signal of luminol varied with the cell concentration based on the impedance ECL mechanism, while the cathodic signal of CdS quantum dots traced the VEGF165 subtype at cell surface by specific aptamer recognition. Based on this, a ratiometric strategy was proposed for accurate cytosensing by eliminating environmental interference. Moreover, by cooperating these two signals, a novel strategy was developed for direct evaluation of the VEGF165 subtype, further realizing rapid drug screening and subtype assessment on different cell lines. This work not only opens up the promising application of MOGs as an effective catalyst matrix but also develops reliable cell assays and protein subtype identification for clinical diagnosis and research.

Fight for carbon neutrality with state-of-the-art negative carbon emission technologies.

After the Industrial Revolution, the ever-increasing atmospheric CO2 concentration has resulted in significant problems for human beings. Nearly all countries in the world are actively taking measures to fight for carbon neutrality. In recent years, negative carbon emission technologies have attracted much attention due to their ability to reduce or recycle excess CO2 in the atmosphere. This review summarizes the state-of-the-art negative carbon emission technologies, from the artificial enhancement of natural carbon sink technology to the physical, chemical, or biological methods for carbon capture, as well as CO2 utilization and conversion. Finally, we expound on the challenges and outlook for improving negative carbon emission technology to accelerate the pace of achieving carbon neutrality.

Advanced nanomaterials for modulating Alzheimer's related amyloid aggregation.

Alzheimer's disease (AD) is a common neurodegenerative disease that brings about enormous economic pressure to families and society. Inhibiting abnormal aggregation of Aß and accelerating the dissociation of aggregates is treated as an effective method to prevent and treat AD. Recently, nanomaterials have been applied in AD treatment due to their excellent physicochemical properties and drug activity. As a drug delivery platform or inhibitor, various excellent nanomaterials have exhibited potential in inhibiting Aß fibrillation, disaggregating, and clearing mature amyloid plaques by enhancing the performance of drugs. This review comprehensively summarizes the advantages and disadvantages of nanomaterials in modulating amyloid aggregation and AD treatment. The design of various functional nanomaterials is discussed, and the strategies for improved properties toward AD treatment are analyzed. Finally, the challenges faced by nanomaterials with different dimensions in AD-related amyloid aggregate modulation are expounded, and the prospects of nanomaterials are proposed.

Understanding the Synergistic Oxidation in Dichalcogenides through Electrochemiluminescence Blinking at Millisecond Resolution.

The oxidation of transition metal dichalcogenides (TMDCs) has been extensively studied and applied in electronics, optics, and energy sources because of its tunable structure and performance. However, due to the lack of appropriate technology, dynamically observe the oxidation process remains an arduous task. Herein, the synergistic oxidation between edge and basal plane in molybdenum disulfide (MoS2 ) is observed through electrogenerated chemiluminescence (ECL) blinking with a millisecond resolution. In addition, the ECL method provides a simple, convenient, and quick way to judge structural changes. The transient elevation of the ECL intensity proved the intermittent doping of oxygen at MoS2 , which generates O-atom active sites. High ECL intensity enhanced from the produced hydroperoxide intermediates eases the monitoring of MoS2 particles. Further study shows that the formation of sulfur vacancies at MoS2 , by the edge activation of hydrogen peroxide and the migration of oxygen to the basal plane, is more conducive to oxygen doping that favors the formation of MoOMo as new active sites to induce bursts. The revealing of sulfur vacancy-governed blinking from MoS2 indicates a complex interaction between oxygen and MoS2 . The same phenomenon is observed on tungsten disulfide (WS2 ), which provides new information about the oxidation feature of 2D dichalcogenides.