Isomerization Engineering of Oxygen-Enriched Carbon Quantum Dots for Efficient Electrochemical Hydrogen Peroxide Production.

Hydrogen peroxide (H2O2) has emerged as a kind of multi-functional green oxidants with extensive industrial utility. Oxidized carbon materials exhibit promises as electrocatalysts in the two-electron (2e-) oxygen reduction reaction (ORR) for H2O2 production. However, the precise identification and fabrication of active sites that selectively yield H2O2 present a serious challenge. Herein, a structural engineering strategy is employed to synthesize oxygen-doped carbon quantum dots (o-CQD) for the 2e- ORR. The surface electronic structure of the o-CQDs is systematically modulated by varying isomerization precursors, thereby demonstrating excellent electrocatalyst performance. Notably, o-CQD-3 emerges as the most promising candidate, showcasing a remarkable H2O2 selectivity of 96.2% (n = 2.07) at 0.68 V versus RHE, coupled with a low Tafel diagram of 66.95 mV dec-1. In the flow cell configuration, o-CQD-3 achieves a H2O2 productivity of 338.7 mmol gcatalyst -1 h-1, maintaining consistent production stability over an impressive 120-hour duration. Utilizing in situ technology and density functional theory calculations, it is unveil that edge sites of o-CQD-3 are facilely functionalized by C-O-C groups under alkaline ORR conditions. This isomerization engineering approach advances the forefront of sustainable catalysis and provides a profound insight into the carbon-based catalyst design for environmental-friendly chemical synthesis processes.

Oxide-Derived Bismuth as an Efficient Catalyst for Electrochemical Reduction of Flue Gas.

Post-combustion flue gas (mainly containing 5-40% CO2 balanced by N2 ) accounts for about 60% global CO2 emission. Rational conversion of flue gas into value-added chemicals is still a formidable challenge. Herein, this work reports a ß-Bi2 O3 -derived bismuth (OD-Bi) catalyst with surface coordinated oxygen for efficient electroreduction of pure CO2 , N2, and flue gas. During pure CO2 electroreduction, the maximum Faradaic efficiency (FE) of formate reaches 98.0% and stays above 90% in a broad potential of 600 mV with a long-term stability of 50 h. Additionally, OD-Bi achieves an ammonia (NH3 ) FE of 18.53% and yield rate of 11.5 µg h-1 mgcat -1 in pure N2 atmosphere. Noticeably, in simulated flue gas (15% CO2 balanced by N2 with trace impurities), a maximum formate FE of 97.3% is delivered within a flow cell, meanwhile above 90% formate FEs are obtained in a wide potential range of 700 mV. In-situ Raman combined with theory calculations reveals that the surface coordinated oxygen species in OD-Bi can drastically activate CO2 and N2 molecules by selectively favors the adsorption of *OCHO and *NNH intermediates, respectively. This work provides a surface oxygen modulation strategy to develop efficient bismuth-based electrocatalysts for directly reducing commercially relevant flue gas into valuable chemicals.

Thermostability enhancement of polyethylene terephthalate degrading PETase using self- and nonself-ligating protein scaffolding approaches.

Polyethylene terephthalate (PET) hydrolase enzymes show promise for enzymatic PET degradation and green recycling of single-use PET vessels representing a major source of global pollution. Their full potential can be unlocked with enzyme engineering to render activities on recalcitrant PET substrates commensurate with cost-effective recycling at scale. Thermostability is a highly desirable property in industrial enzymes, often imparting increased robustness and significantly reducing quantities required. To date, most engineered PET hydrolases show improved thermostability over their parental enzymes. Here, we report engineered thermostable variants of Ideonella sakaiensis PET hydrolase enzyme (IsPETase) developed using two scaffolding strategies. The first employed SpyCatcher-SpyTag technology to covalently cyclize IsPETase, resulting in increased thermostability that was concomitant with reduced turnover of PET substrates compared to native IsPETase. The second approach using a GFP-nanobody fusion protein (vGFP) as a scaffold yielded a construct with a melting temperature of 80°C. This was further increased to 85°C when a thermostable PETase variant (FAST PETase) was scaffolded into vGFP, the highest reported so far for an engineered PET hydrolase derived from IsPETase. Thermostability enhancement using the vGFP scaffold did not compromise activity on PET compared to IsPETase. These contrasting results highlight potential topological and dynamic constraints imposed by scaffold choice as determinants of enzyme activity.

Elucidation of the synergistic effects of 3d metal (M = Cu, Co, and Ni) dopants and terminations (T = -O- and -OH) of Ti3C2Tx MXenes for urea adsorption ability via DFT calculations and experiments.

Dialysis is an artificial process to remove excess urea toxins from the body through adsorption or conversion. Urea adsorption by emergent 2D materials such as MXenes is one probable approach. Based on density functional theory (DFT) studies, the surface of Ti3C2Tx (T = -O- and -OH) MXenes is not optimum for urea adsorption. Therefore, functionalization with 3d metal dopants (Cu, Co, and Ni) is proposed to improve their urea adsorption ability. DFT calculations indicate that oxygen-terminated Ti3C2O2 has a much better urea adsorption ability when doped with Cu, Co, and Ni, with adsorption energy (Eads) values of -2.11 eV, -1.90 eV and -1.72 eV, respectively. These adsorption energies are much more favourable than that of the undoped one (Eads = -0.52 eV). To verify the calculation results, MILD Ti3C2Tx, or MXenes synthesized via the safer and easier minimally intensive layer delamination (MILD) method, were utilized to simulate Ti3C2O2 since they have -O- termination as the dominant species. Experimentally, the adsorption studies found that low concentration of Cu, Co, and Ni on MILD Ti3C2Tx showed a urea removal efficiency of 21.9%, 6.0% and 0.2%, respectively, much better than 0% removal efficiency of unfunctionalized Ti3C2Tx. Therefore, both DFT calculations and experiments showed that various metal functionalized MXenes have a similar trend for urea adsorption, highlighting the feasibility of using the computational approach to predict urea adsorption and further opening a new promising direction for the urea adsorption. Finally, this study is also the first to examine synergistic effects of metal dopants and surface terminations on MXenes for urea adsorption.

Two Birds with One Stone: FeS2@C Yolk-Shell Composite for High-Performance Sodium-Ion Energy Storage and Electromagnetic Wave Absorption.

Cost-effective material with a rational design is significant for both sodium-ion batteries (SIBs) and electromagnetic wave (EMW) absorption. Herein, we report an elaborate yolk-shell FeS2@C nanocomposite as a promising material for application in both SIBs and EMW absorption. When applied as an anode material in SIBs, the yolk-shell structure not only facilitates a fast electron transport and shortens Na ion diffusion paths but also eases the huge volume change of FeS2 during repeated discharge/charge processes. The as-developed FeS2@C exhibits a high specific capacity of 616 mA h g-1 after 100 cycles at 0.1 A g-1 with excellent rate performance. Furthermore, owing to the significant cavity and interfacial effects enabled by yolk-shell structuring, the FeS2@C nanocomposite delivers excellent EMW absorption properties with a strong reflection loss (-45 dB with 1.45 mm matching thickness) and a broad 15.4 GHz bandwidth. This work inspires the development of high-performance bifunctional materials.

Double-Chain Cationic Surfactants: Swelling, Structure, Phase Transitions and Additive Effects.

Double-chain amphiphilic compounds, including surfactants and lipids, have broad significance in applications like personal care and biology. A study on the phase structures and their transitions focusing on dioctadecyldimethylammonium chloride (DODAC), used inter alia in hair conditioners, is presented. The phase behaviour is dominated by two bilayer lamellar phases, Lß and Lα, with "solid" and "melted" alkyl chains, respectively. In particular, the study is focused on the effect of additives of different polarity on the phase transitions and structures. The main techniques used for investigation were differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering (SAXS and WAXS). From the WAXS reflections, the distance between the alkyl chains in the bilayers was obtained, and from SAXS, the thicknesses of the surfactant and water layers. The Lα phase was found to have a bilayer structure, generally found for most surfactants; a Lß phase made up of bilayers with considerable chain tilting and interdigitation was also identified. Depending mainly on the polarity of the additives, their effects on the phase stabilities and structure vary. Compounds like urea have no significant effect, while fatty acids and fatty alcohols have significant effects, but which are quite different depending on the nonpolar part. In most cases, Lß and Lα phases exist over wide composition ranges; certain additives induce transitions to other phases, which include cubic, reversed hexagonal liquid crystals and bicontinuous liquid phases. For a system containing additives, which induce a significant lowering of the Lß-Lα transition, we identified the possibility of a triggered phase transition via dilution with water.

Pressure-Responsive Two-Dimensional Metal-Organic Framework Composite Membranes for CO2 Separation.

The regulation of permeance and selectivity in membrane systems may allow effective relief of conventional energy-intensive separations. Here, pressure-responsive ultrathin membranes (≈100 nm) fabricated by compositing flexible two-dimensional metal-organic framework nanosheets (MONs) with graphene oxide nanosheets for CO2 separation are reported. By controlling the gas permeation direction to leverage the pressure-responsive phase transition of the MONs, CO2 -induced gate opening and closing behaviors are observed in the resultant membranes, which are accompanied with the sharp increase of CO2 permeance (from 173.8 to 1144 gas permeation units) as well as CO2 /N2 and CO2 /CH4 selectivities (from 4.1 to 22.8 and from 4 to 19.6, respectively). The flexible behaviors and separation mechanism are further elucidated by molecular dynamics simulations. This work establishes the relevance of structural transformation-based framework dynamics chemistry in smart membrane systems.

Multiscale Self-Assembly of a Phenyl-Flanked Diketopyrrolopyrrole Derivative: A Solution-Processable Building Block for π-Conjugated Supramolecular Polymers.

We report a solution-processable π-conjugated molecular building block (denoted as PhDPP) consisting of a rigid and planar core of phenyl-flanked diketopyrrolopyrrole and "soft" branched alkoxy chains that endow the solubility in a variety of organic solvents. Intermolecular hydrogen bonding in PhDPP was revealed in nonpolar solvents above a threshold of concentration and below a critical point of temperature. The strong intermolecular interaction mainly contributed by the hydrogen-bonding and π-π interaction between PhDPP molecules promoted the formation of supramolecular polymeric structures in both solution and solid states and at interfaces. The supramolecular polymeric properties enabled solution-based processing of PhDPP under a variety of conditions into different structures including fibers and uniform thin films. The structure-property relationship that we established in the present system of PhDPP from the molecular to supramolecular level will be important to solution-process this type of H-bonding π-conjugated molecules for a variety of applications such as optoelectronic devices.

Elucidating the relationship between crystallo-chemistry and optical properties of CIGS nanocrystals.

The performance of solar cells fabricated using Cu(In,Ga)(S,Se)2 nanocrystal (NC) inks synthesized using the hot injection method has yielded efficiencies up to 12% recently. The efficiency of these devices is highly dependent on the chemical composition and crystallographic quality of the NCs. The former has been extensively discussed as it can be easily correlated to the optical properties of the film, but detailed crystallographic structure of these NCs has scarcely been discussed and it can influence both the optical and electrical properties. Hence both chemical composition and crystal structure should be explored for these NCs in order for this material to be further developed for application in thin film solar cells. In this work, a thorough investigation of the composition and crystal structure of CuIn x Ga1-x Se2 NCs synthesized using the hot injection method over the entire composition range (0 ≤ x ≤ 1) has been conducted. Raman spectroscopy of the NCs complements the information derived from x-ray diffraction (XRD) and electron probe microanalysis (EPMA). EPMA, which was carried out for the first time, indicates good controllability of the NC Ga/(In + Ga) ratio using this synthesis method. Raman spectroscopy reveals that CuInSe2 NCs are a mixture of chalcopyrite and sphalerite with disordered cations, whereas CuGaSe2 NCs are purely chalcopyrite. The lattice parameters determined from XRD were found to deviate from those calculated using Vegard's law for all compositions. Hence, it can be deduced that the lattice is distorted in the crystal. The optical and electrochemical band gap of CuIn x Ga1-x Se2 NCs increases as the Ga content increases. The energy band gap deviates from the theoretical values, which could be related to the contribution from cation disordering and strain. These results help to tailor the opto-electrical properties of semiconductors, which inherently depend on the crystalline quality, strain and composition.

Effect of Zinc Incorporation on the Performance of Red Light Emitting InP Core Nanocrystals.

This report presents a systematic study on the effect of zinc (Zn) carboxylate precursor on the structural and optical properties of red light emitting InP nanocrystals (NCs). NC cores were assessed using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), energy-dispersive X-ray spectroscopy (EDX), and high-resolution transmission electron microscopy (HRTEM). When moderate Zn:In ratios in the reaction pot were used, the incorporation of Zn in InP was insufficient to change the crystal structure or band gap of the NCs, but photoluminescence quantum yield (PLQY) increased dramatically compared with pure InP NCs. Zn was found to incorporate mostly in the phosphate layer on the NCs. PL, PLQY, and time-resolved PL (TRPL) show that Zn carboxylates added to the precursors during NC cores facilitate the synthesis of high-quality InP NCs by suppressing nonradiative and sub-band-gap recombination, and the effect is visible also after a ZnS shell is grown on the cores.

Correlation between blend morphology and recombination dynamics in additive-added P3HT:PCBM solar cells.

The addition of a small amount of high boiling point solvent in organic donor/acceptor blends to control their morphology is a viable approach to enhance the power conversion efficiency of bulk heterojunction (BHJ) organic solar cells. Herein, through transient absorption spectroscopy (TAS) correlated with physical characterizations and device studies, we investigate the effects of a family of thiol-based additives (i.e., 1,5-pentanedithiol (PDT), 1,6-hexanedithiol (HDT) and 1,8-octanedithiol (ODT)) in P3HT:PCBM blend films in a bid to establish a morphology-function-charge dynamics relationship with their photovoltaic performances. The performance of solar cell devices (ηHDT = 2.8%, ηODT = 2.8%, ηPDT = 1.7%) is related to the additive-induced phase separation and the degree of ordering of P3HT. TAS uncovers a more efficient initial exciton and polaron generation in the additive-treated blend samples compared to the non-additive treated control sample. HDT and ODT-added blends exhibit decay dynamics and performances similar to those of the thermally annealed samples. However, the PDT-added blend exhibits a strong trap-assisted recombination in the subsequent nanosecond-microsecond timescales. We attribute this to the loss of charge carriers in the larger isolated P3HT domains due to the lack of percolation paths to the electrode. Our findings illustrate that understanding the complex interplay of the crystalline order, intermixed phases and percolation pathways is key to optimizing the performance of thermal-annealing free, additive-treated organic solar cells.

Reducing mass-transport limitations in cobalt-electrolyte-based dye-sensitized solar cells by photoanode modification.

Mass transport has been identified as a limiting problem in the photovoltaic performance of dye-sensitized solar cells based on electrolytes consisting of ionic liquids or cobalt complexes. A mixed TiO2 macroporous-mesoporous morphology employed as photoanode is demonstrated to assist the diffusion of electrolytes with higher viscosity or consisting of bulky redox mediators, such as cobalt di-tert-butyl bipyridine [Co(dtb)3](2+/3+). This morphology with large pores improves the non-linearity of photocurrent response to light intensity indicating better diffusion. The incorporated sub-micrometer pores also reduce recombination and decrease diffusion resistance, as revealed by electrochemical impedance spectroscopy.

Phase-selective synthesis of Cu2ZnSnS4 nanocrystals using different sulfur precursors.

Cu2ZnSnS4 (CZTS) holds great promises as an absorber material for sustainable and low cost thin film solar cells. Kesterite and wurtzite are two common phases of CZTS. Until now, the synthesis and the growth of both phases are not clearly understood. In this work, kesterite CZTS nanoparticles, wurtzite CZTS nanoparticles as well as CZTS particles with a mixture of both structures were prepared by using elemental sulfur, 1-dodecanethiol, and thioacetamide, respectively. Time dependent studies were conducted and the reaction rate of sulfur source was found to be the key factor in determining the phase formation. Elemental sulfur reacts with oleylamine to produce highly reactive small molecule H2S, which leads to the formation of kesterite phase. The reaction pathways of the long alkane chain 1-dodecanethiol yield the formation of wurtzite phase via a binary phase. Thioacetamide yields a mixture of kesterite and wurtzite phase in the final product. The optical and electrical properties of kesterite and wurtzite CZTS were also evaluated.

Polymer nanofibers: preserving nanomorphology in ternary blend organic photovoltaics.

The morphology of donor-acceptor blends holds the key to good performance through the balancing of good exciton dissociation efficiency and interconnectivity for good charge collection. In this work, the good morphology is preserved in ternary blend systems through the use of poly(3-hexylthiophene) (P3HT) nanofibers. The iridium(III)-based metal complex is incorporated in P3HT-PCBM blends as a triplet exciton sensitizer in the bulk heterojunction (BHJ) organic photovoltaics (OPV). The devices using triplet-sensitized ternary blends of P3HT experience a significant degradation in performance, a tendency further aggravated by thermal treatment. This is due to disruption in the morphology thus affecting charge generation and collection. In order to overcome these morphological issues and to circumvent the restriction due to the crystallization of the polymers, here we demonstrate the use of pre-assembled nanofibers in these ternary blends. The concept of stabilizing the nanomorphology of the blend material through the use of nanofibers can also be applied to other ternary systems.

Synthesis of two-dimensional transition-metal phosphates with highly ordered mesoporous structures for lithium-ion battery applications.

Materials with ordered mesoporous structures have shown great potential in a wide range of applications. In particular, the combination of mesoporosity, low dimensionality, and well-defined morphology in nanostructures may exhibit even more attractive features. However, the synthesis of such structures is still challenging in polar solvents. Herein, we report the preparation of ultrathin two-dimensional (2D) nanoflakes of transition-metal phosphates, including FePO4, Mn3(PO4)2, and Co3(PO4)2, with highly ordered mesoporous structures in a nonpolar solvent. The as-obtained nanoflakes with thicknesses of about 3.7 nm are constructed from a single layer of parallel-packed pore channels. These uniquely ordered mesoporous 2D nanostructures may originate from the 2D assembly of cylindrical micelles formed by the amphiphilic precursors in the nonpolar solvent. The 2D mesoporous FePO4 nanoflakes were used as the cathode for a lithium-ion battery, which exhibits excellent stability and high rate capabilities.

Operando Electrodeposition of Nonprecious Metal Copper Nanocatalysts on Low-Dimensional Support Materials for Nitrate Reduction Reactions.

Supported nonprecious metal catalysts such as copper (Cu) are promising replacements for Pt-based catalysts for a wide range of energy-related electrochemical reactions. Direct electrochemical deposition is one of the most straightforward and versatile methods to synthesize supported nonprecious metal catalysts. However, further advancement in the design of supported nonprecious metal catalysts requires a detailed mechanistic understanding of the interplay between kinetics and thermodynamics of the deposition phenomena under realistic reaction conditions. Here, we study the electrodeposition of Cu on carbon nanotubes and graphene derivatives under electrochemical conditions using in situ liquid cell transmission electron microscopy (TEM). By combining real-time imaging, electrochemical measurements, X-ray photoelectron spectroscopy (XPS), and finite-element analysis (FEA), we show that low-dimensional support materials, especially carbon nanotubes, are excellent for generating uniform and finely dispersed platinum group metal-(PGM)-free catalysts under mild electrochemical conditions. The electrodeposited Cu on graphene and carbon nanotubes is also observed to show good electrochemical activity toward nitrate reduction reactions (NO3RRs), further supported by density functional theory (DFT) calculations. Nitrogen doping plays an important role in guiding nonprecious metal deposition, but its low electrical conductivity may give rise to lower NO3RR activity compared to its nondoped analogue. The development of supported nonprecious metals through interfacial and surface engineering for the design of supported catalysts will substantially reduce the demand for precious metals and generate robust catalysts with better durability, thereby presenting opportunities for solving the critical problems in energy storage and electrocatalysis.

Retinomorphic Color Perception Based on Opponent Process Enabled by Perovskite Bipolar Photodetectors.

The ability to perceive color by the retina can be attributed to both its trichromatic photoreceptors and the antagonistic neural wiring known as the opponent process. While neuromorphic sensors have been shown to demonstrate memory and adaptation capabilities, color perception is still challenging due to the intrinsic lack of spectral selectivity in narrow bandgap semiconductors. Furthermore, research on emulating neural wiring is severely lacking. The combination of halide perovskite materials with a tunable bandgap and a novel bipolar photodetector design emulates the efficiency of the retina in processing color information. The stimuli-responsive material is also responsible for maintaining partial color constancy-an adaptation feature. Leveraging the unique enhancement of color contrasts, an in-sensor data compression and edge detection can also be demonstrated. The color perception, chromatic adaptation, and color contrast enhancement make perovskite bipolar photodetectors a unique example where the sensor and neural wiring can be co-developed in conjunction.

Nanozyme-based colorimetric sensor arrays coupling with smartphone for discrimination and "segmentation-extraction-regression" deep learning assisted quantification of flavonoids.

Achieving rapid, cost effective, and intelligent identification and quantification of flavonoids is challenging. For fast and uncomplicated flavonoid determination, a sensing platform of smartphone-coupled colorimetric sensor arrays (electronic noses) was developed, relying on the differential competitive inhibition of hesperidin, nobiletin, and tangeretin on the oxidation reactions of nanozymes with a 3,3',5,5'-tetramethylbenzidine substrate. First, density functional theory calculations predicted the enhanced peroxidase-like activities of CeO2 nanozymes after doping with Mn, Co, and Fe, which was then confirmed by experiments. The self-designed mobile application, Quick Viewer, enabled a rapid evaluation of the red, green, and blue values of colorimetric images using a multi-hole parallel acquisition strategy. The sensor array based on three channels of CeMn, CeFe, and CeCo was able to discriminate between different flavonoids from various categories, concentrations, mixtures, and the various storage durations of flavonoid-rich Citri Reticulatae Pericarpium through a linear discriminant analysis. Furthermore, the integration of a "segmentation-extraction-regression" deep learning algorithm enabled single-hole images to be obtained by segmenting from a 3 × 4 sensing array to augment the featured information of array images. The MobileNetV3-small neural network was trained on 37,488 single-well images and achieved an excellent predictive capability for flavonoid concentrations (R2 = 0.97). Finally, MobileNetV3-small was integrated into a smartphone as an application (Intelligent Analysis Master), to achieve the one-click output of three concentrations. This study developed an innovative approach for the qualitative and simultaneous multi-ingredient quantitative analysis of flavonoids.

Synthesis of Cu2SnSe3 nanocrystals for solution processable photovoltaic cells.

This paper describes the synthesis of ternary chalcogenide Cu(2)SnSe(3) nanocrystals as an alternative solar absorber material to conventional quaternary CuIn(x)Ga(1-x)Se(2). We used the hot coordination solvent method with hexadecylamine as the capping ligand for the first time for this material system. Using a variety of characterization techniques, such as X-ray diffraction, selected area electron diffraction, convergent beam electron diffraction, and Raman spectroscopy, the nanocrystals were found to be monoclinic Cu(2)SnSe(3) with an optical energy band gap of 1.3 eV and have a narrow size distribution. These nanocrystals are shown to be photosensitive in the range of wavelengths corresponding to the solar spectrum, which makes them highly promising as alternative photon absorber materials for photovoltaic applications.

Flexible Wet-Spun PEDOT:PSS Microfibers Integrating Thermal-Sensing and Joule Heating Functions for Smart Textiles.

Multifunctional fiber materials play a key role in the field of smart textiles. Temperature sensing and active thermal management are two important functions of smart fabrics, but few studies have combined both functions in a single fiber material. In this work, we demonstrate a temperature-sensing and in situ heating functionalized conductive polymer microfiber by exploiting its high electrical conductivity and thermoelectric properties. The conductive polymer microfibers were prepared by wet-spinning the PEDOT:PSS aqueous dispersion with ionic liquid additives, which was used to enhance the electrical and mechanical properties of the final microfibers. The thermoelectric properties of these microfibers were further studied. Due to their excellent flexibility and mechanical properties, these fibers can be easily integrated into commercial fabrics for the manufacture of smart textiles through knitting. We further demonstrated a smart glove with integrated temperature-sensing and in situ heating functions, and further explored thermoelectric fiber-based temperature-sensing array fabric. These works combine the thermoelectric properties and heating function of conductive polymer fibers, providing new insights that enable further development of high-performance, multifunctional wearable smart textiles.