Electron Deficiency is More Important than Conductivity in C-N Coupling for Electrocatalytic Urea Synthesis.

The electrocatalytic C-N coupling from CO2 and nitrate emerges as one of the solutions for waste upgrading and urea synthesis. In this work, we constructed electron-deficient Cu sites by the strong metal-polymer semiconductor interaction, to boost efficient and durable urea synthesis. In situ Raman spectroscopy identified the existence of electron-deficient Cu sites and was able to withstand electrochemical reduction conditions. Operando synchrotron-radiation Fourier transform infrared spectroscopy and theoretical calculations disclosed the vital role of electron-deficient Cu in adsorption and C-N coupling of oxygen-containing species. The electron-deficient Cu displayed a high urea yield rate of 255.0 mmol h-1 g-1 at -1.4 V versus the reversible hydrogen electrode and excellent electrochemical durability, superior than that of non-electron-deficient counterpart with conductive carbon material as the support. It can be concluded that the regulation of site electronic structure is more important than the optimization of catalyst conductive properties in the C-N coupling reactions.

Evaluation of potentially harmful Maillard reaction products in different types of commercial formulae.

Pasteurisation and spray drying are critical steps to ensure the safety and shelf-life of formulae, but these treatments also induce formation of some potentially harmful Maillard reaction products. In this study, the occurrence of potentially harmful Maillard reaction products and proximate compositions in different commercial formulae were analysed. Our results showed that infant formulae had significantly higher concentrations of furosine, Nε-(carboxymethyl)lysine (CML) and Nε-(carboxyethyl)lysine (CEL) than follow-on/toddler formula. Specialty formulae had higher concentrations of glyoxal and CML than other types of formulae. Correlation analysis indicated that concentrations of 5-hydroxymethylfurfural, 3-deoxyglucosone, CML and CEL were closely related to fat contents. These results provided insight into concentrations of potentially harmful Maillard reaction products in different types of formulae and provide a theoretical basis for further optimisation of processing.

Methods for assessing spillover effects between concurrent green initiatives.

This research presents the methods that are used to examine the dynamics and potential spillover effects of various global environmental conservation programs. We specifically show the data and models that we use to analyze the interactions and mutual influences between the U.S.'s Conservation Reserve Program (CRP) and Environmental Quality Incentives Program (EQIP), as well as those between China's Grain-to-Green Program (GTGP) and Forest Ecological Benefit Compensation (FEBC). Additionally, this study illustrates information about global initiatives, their interconnected impacts, and the associated policy strategies for environmental conservation. By utilizing multivariate regression, logistic regression, eigenvector spatial filtering, and scenario modeling, the research aims to understand the collective influence of these initiatives on broader environmental objectives. The findings of this study provide valuable insights for improving conservation policy designs and effectiveness.•Multivariate and logistic regression analyses to dissect global environmental conservation program interactions and mutual influences.•Eigenvector spatial filtering to address spatial autocorrelation and enhance the accuracy of the model results and our interpretations.•Scenario modeling to project potential future outcomes and impacts.

Structural changes of rice starch-anthocyanins complexes (V-type) and its impact on gut microbiotas and potential metabolic pathways during in vitro fermentation.

This study explored the differences in the in vitro fermentation properties of rice starch (RS) and rice starch-anthocyanins complexes (RS-A). Structural characterization suggested that RS and RS-A complexes showed a V-type crystalline structure. The degree of order (DO) and degree of double helix (DD) values of RS and RS-A complexes were enhanced after fermentation. Moreover, the RS-A complexes could improve the relative abundance of Bacteroidetes, Ruminococcaceae, and up-regulate gut microbiota diversity to maintain gut homeostasis. Relative abundance of potential metabolic pathways, such as energy metabolism, digestion system, and carbohydrate degradation overexpressed in the presence of RS-A complexes. The results demonstrated that the RS-A complexes had slower fermentation rates contributing to the transport of the formed short-chain fatty acid (SCFA) to the end of the colon and that the crystallinity might be a factor influencing the utilization of the starch matrix by the gut microbiota for SCFA formation.

Design of Single-Atom Catalysts for E lectrocatalytic Nitrogen Fixation.

The Electrochemical nitrogen reduction reaction (ENRR) can be used to solve environmental problems as well as energy shortage. However, ENRR still faces the problems of low NH3 yield and low selectivity. The NH3 yield and selectivity in ENRR are affected by multiple factors such as electrolytic cells, electrolytes, and catalysts, etc. Among these catalysts are at the core of ENRR research. Single-atom catalysts (SACs) with intrinsic activity have become an emerging technology for numerous energy regeneration, including ENRR. In particular, regulating the microenvironment of SACs (hydrogen evolution reaction inhibition, carrier engineering, metal-carrier interaction, etc.) can break through the limitation of intrinsic activity of SACs. Therefore, this Review first introduces the basic principles of NRR and outlines the key factors affecting ENRR. Then a comprehensive summary is given of the progress of SACs (precious metals, non-precious metals, non-metallic) and diatomic catalysts (DACs) in ENRR. The impact of SACs microenvironmental regulation on ENRR is highlighted. Finally, further research directions for SACs in ENRR are discussed.

Dual-functional thermal management textiles for dynamic temperature regulation based on ultra-stretchable spiral conductive composite yarn with 500%-strain thermal stability and durability.

Next-generation personal thermal management (PTM) textiles for daily routine environments are attracting extensive attention. However, challenges remain in developing multifunctional PTM textiles that are comfortable to wear, have motion stability and environmental adaptability. Herein, a novel design for fabricating a sandwich-structure PTM textile based on an ultra-stretchable spiral conductive composite yarn (SCCY) with strain-electric stability is proposed. An SCCY composed of carbon nanotubes (CNTs)/polyvinyl pyrrolidone (PVP)/waterborne polyurethane (WPU) and a drawn textured yarn (DTY) is fabricated through a dip-twisting and shaping process. The PVP not only facilitates the interfacial bonding between CNTs and yarn, but also constructs strong hydrogen bond interactions with WPU, resulting in improved structure stability and robust electrical performance. Benefitting from the optimized spiral and composite structure, the SCCY exhibits a fast thermal response (130 °C within 8 s), long-term durability (1500 cycles), and superior thermal stability under large deformation (ΔT/T0 ≈ 8.4%, under 500%). By assembling a stretchable electrothermal fabric based on SCCYs with an elastic fabric and thermochromic layer, temperature visualization and dynamic temperature regulation are integrated into the textile. This multifunctional PTM textile not only features dual thermal regulation modes of radiant cooling and Joule heating, but also maintains flexibility, breathability, and excellent stretchability, which provides broad application prospects in next-generation wearable devices.

Oxygen-Bridged Copper-Iron Atomic Pair as Dual-Metal Active Sites for Boosting Electrocatalytic NO Reduction.

Electrocatalytic reduction of nitric oxide (NO) to ammonia (NH3 ) is a promising approach to NH3 synthesis. However, due to the lack of efficient electrocatalysts, the performance of electrocatalytic NO reduction reaction (NORR) is far from satisfactory. Herein, it is reported that an atomic copper-iron dual-site electrocatalyst bridged by an axial oxygen atom (OFeN6 Cu) is anchored on nitrogen-doped carbon (CuFe DS/NC) for NORR. The CuFe DS/NC can significantly enhance the electrocatalytic NH3 synthesis performance (Faraday efficiency, 90%; yield rate, 112.52 µmol cm-2  h-1 ) at -0.6 V versus RHE, which is dramatically higher than the corresponding Cu single-atom, Fe single-atom and all NORR single-atom catalysts in the literature so far. Moreover, an assembled proof-of-concept Zn-NO battery using CuFe DS/NC as the cathode outputs a power density of 2.30 mW cm-2 and an NH3 yield of 45.52 µg h-1  mgcat -1 . The theoretical calculation result indicates that bimetallic sites can promote electrocatalytic NORR by changing the rate-determining step and accelerating the protonation process. This work provides a flexible strategy for efficient sustainable NH3 synthesis.

Electrocatalytic Urea Synthesis with 63.5 % Faradaic Efficiency and 100 % N-Selectivity via One-step C-N coupling.

Electrocatalytic urea synthesis via coupling N2 and CO2 provides an effective route to mitigate energy crisis and close carbon footprint. However, the difficulty on breaking N≡N is the main reason that caused low efficiencies for both electrocatalytic NH3 and urea synthesis, which is the bottleneck restricting their industrial applications. Herein, a new mechanism to overcome the inert of the nitrogen molecule was proposed by elongating N≡N instead of breaking N≡N to realize one-step C-N coupling in the process for urea production. We constructed a Zn-Mn diatomic catalyst with axial chloride coordination, Zn-Mn sites display high tolerance to CO poisoning and the Faradaic efficiency can even be increased to 63.5 %, which is the highest value that has ever been reported. More importantly, negligible N≡N bond breakage effectively avoids the generation of ammonia as intermediates, therefore, the N-selectivity in the co-electrocatalytic system reaches100 % for urea synthesis. The previous cognition that electrocatalysts for urea synthesis must possess ammonia synthesis activity has been broken. Isotope-labelled measurements and Operando synchrotron-radiation Fourier transform infrared spectroscopy validate that activation of N-N triple bond and nitrogen fixation activity arise from the one-step C-N coupling process of CO species with adsorbed N2 molecules.

Discrepancy of Effective Water Diffusivities Determined from Dynamic Vapor Sorption Measurements with Different Relative Humidity Step Sizes: Observations from Cereal Materials.

Water diffusivity, a critical parameter for cereal processing design and quality optimization, is usually concentration-dependent. dynamic vapor sorption (DVS) system provides an approach to establishing the relationship between water concentration and diffusivity. However, the usual relative humidity (RH) jump during practical sorption processes is usually greater than that adopted in DVS measurements. Water vapor sorption kinetics of glutinous rice grains, glutinous rice flour and wheat flour dough films were measured using the DVS system to verify if varying RH step sizes can obtain identical diffusivities within the same range. The effective diffusivities were determined according to Fick's second law. The results revealed that increasing RH step size led to a higher estimated diffusivity, regardless of whether the water concentration gradient or potential chemical gradient was considered a driving force for water diffusion. This finding was further confirmed by a linear RH scanning DVS measurement. The water concentration-dependent diffusivity obtained from a multi-step DVS measurement, according to Fick's second law, will overestimate the required time for practical cereal drying or adsorption. Thus, this paradoxical discrepancy needs a new mass transfer mechanism to be explained.

Hexagonal Cobalt Nanosheets for High-Performance Electrocatalytic NO Reduction to NH3.

Electrocatalytic nitric oxide (NO) reduction not only provides an extremely promising strategy for ambient NH3 generation but also alleviates the artificially disrupted N-cycle balance. However, exploring efficient electrocatalysts to enhance the NO electroreduction performance remains a significant challenge. Herein, a hexagonal-close-packed Co nanosheet (hcp-Co) is prepared and exhibits a high NH3 yield of 439.50 µmol cm-2 h-1 and a Faraday efficiency of 72.58%, outperforming the face-centered cubic phase of the Co nanosheet (fcc-Co) and most reported electrocatalysts. Through the combination of density functional theory calculations and NO temperature-programmed desorption experiments, the superior catalytic NO reduction reaction (NORR) activity on the hcp-Co can be attributed to the unique electron structures and proton shuttle effect. A proof-of-concept device of Zn-NO batteries using the hcp-Co as the cathode is assembled and shows a power density of 4.66 mW cm-2, which is superior to the reported performance in the literature so far.

C-Bound or O-Bound Surface: Which One Boosts Electrocatalytic Urea Synthesis?

The electrocatalytic C-N coupling from carbon dioxide and nitrate under ambient conditions is kind of sustainable and promising alternative method for urea synthesis. To date, the influence of catalyst surface properties on molecular adsorption configuration and electrocatalytic urea synthesis activity is unclear. In this work, we proposed that the urea synthesis activity is closely linked with the localized surface charge on bimetallic electrocatalysts, it is found that a negatively charged surface induces C-bound path and boosts urea synthesis. The urea yield rate can reach 13.1 mmol g-1 h-1 on negatively charged Cu97 In3 -C, which is about 13 times that of positively charged Cu30 In70 -C counterpart with O-bound surface. This conclusion also applies to Cu-Bi and Cu-Sn systems. The molecular modification shifts the surface of Cu97 In3 -C to positively charged state, which leads to a sharp decline in urea synthesis performance. We demonstrated that the C-bound surface is more favorable than O-bound one to boost electrocatalytic urea synthesis.

Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis.

Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of carbon footprint closing, valorization of waste, and sustainable manufacture of urea. However, the identification of catalytic active sites and the design of efficient electrocatalysts remain a challenge. Herein, the synthesis of urea catalyzed by copper single atoms decorated on a CeO2 support (denoted as Cu1 -CeO2 ) is reported. The catalyst exhibits an average urea yield rate of 52.84 mmol h-1 gcat. -1 at -1.6 V versus reversible hydrogen electrode. Operando X-ray absorption spectra demonstrate the reconstitution of copper single atoms (Cu1 ) to clusters (Cu4 ) during electrolysis. These electrochemically reconstituted Cu4 clusters are real active sites for electrocatalytic urea synthesis. Favorable CN coupling reactions and urea formation on Cu4 are validated using operando synchrotron-radiation Fourier transform infrared spectroscopy and theoretical calculations. Dynamic and reversible transformations of clusters to single-atom configurations occur when the applied potential is switched to an open-circuit potential, endowing the catalyst with superior structural and electrochemical stabilities.

Practical method for improving the accuracy of weakly stressed birefringence detection by circularly polarized instantaneous photoelasticity.

Due to the mismatch between the quarter-wave plate and the wavelength of the light source, the circularly polarized field photoelastic stress analysis method has an impact on the measurement of the phase delay and the stress direction angle. In particular, the measurement of the phase delay is inaccurate for weakly stressed samples with phase delays less than a quarter-wavelength. In this paper, we first give a method for calculating the mismatch value δ, which requires only one air calibration without prior calibration of the parameters of the quarter-wave plate with other equipment. We then introduce δ into the correction process for the phase delay, derive the correction equation, and give a theoretical comparison of the relative error curves. The results show that the correction method can theoretically limit the maximum amount of error. Finally, we have verified the accuracy of the method by measurements of the internal lens stress before and after the correction and by stitching measurements on SiC wafers.

Occurrence and removal of per- and polyfluoroalkyl substances (PFAS) in leachates from incineration plants: A full-scale study.

Municipal solid wastes (MSWs) contain diverse per- and polyfluoroalkyl substances (PFAS), and these substances may leach into leachates, resulting in potential threats to the environment and human health. In this study, leachates from incineration plants with on-site treatment systems were measured for 17 PFAS species, including 13 perfluorocarboxylic acids (PFCAs) and 4 perfluorosulfonic acids (PFSAs). PFAS were detected in all of the raw leachates and finished effluents in concentrations ranging from 7228 to 16,565 ng L-1 and 43 to 184 ng L-1, respectively, with a greater contribution from the short-chain PFAS and PFCAs. The results showed that the existing combined processes (biological treatment and membrane filtration) were effective in decreasing PFAS in the aqueous phase with removal efficiencies over 95%. In addition, correlation analysis suggested that physical entrapment, not biodegradation, was the main means of PFAS reduction in the treatment system. These results filled a gap in the understanding of PFAS occurrence and removal in leachates from incineration plants during the full-scale treatment processes, and demonstrated those leachates were previously under-explored sources of PFAS.

Three-dimensional stitching of stereo-deflectometry based on marker points.

As a non-contact and three-dimensional (3D) mirror surface measurement method, stereo-deflectometry has been developing rapidly in recent years. For solving the problem of the measurement of large surface inclination with traditional stereo-deflectometry, 3D stitching of stereo-deflectometry based on marker points is proposed. In this method, the 3D points in the subregions under different perspectives were measured. Meanwhile, the 3D coordinates of the marker points on the sample table, which were calculated by binocular stereo vision, were used for coarse stitching, and the ICP algorithm was used for fine stitching. In order to verify the 3D stitching algorithm, we built a measurement system for the freeform surface of an ultra-short lens with a diameter of about 100 mm and a steepness of 52.6°. The spherical fitting error of the reflective bowl after stitching is within 60 mm. The experimental results verify the feasibility of the method, leading to potential mass application of stereo-deflectometry in 3D measurement of complex optical surfaces with a large aperture and high steepness.

Identifying and tailoring C-N coupling site for efficient urea synthesis over diatomic Fe-Ni catalyst.

Electrocatalytic urea synthesis emerged as the promising alternative of Haber-Bosch process and industrial urea synthetic protocol. Here, we report that a diatomic catalyst with bonded Fe-Ni pairs can significantly improve the efficiency of electrochemical urea synthesis. Compared with isolated diatomic and single-atom catalysts, the bonded Fe-Ni pairs act as the efficient sites for coordinated adsorption and activation of multiple reactants, enhancing the crucial C-N coupling thermodynamically and kinetically. The performance for urea synthesis up to an order of magnitude higher than those of single-atom and isolated diatomic electrocatalysts, a high urea yield rate of 20.2 mmol h-1 g-1 with corresponding Faradaic efficiency of 17.8% has been successfully achieved. A total Faradaic efficiency of about 100% for the formation of value-added urea, CO, and NH3 was realized. This work presents an insight into synergistic catalysis towards sustainable urea synthesis via identifying and tailoring the atomic site configurations.

Heterogeneous-Interface-Enhanced Adsorption of Organic and Hydroxyl for Biomass Electrooxidation.

Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) provides an efficient way to obtain high-value-added biomass-derived chemicals. Compared with other transition metal oxides, CuO exhibits poor oxygen evolution reaction performance, leading to high Faraday efficiency for HMF oxidation. However, the weak adsorption and activation ability of CuO to OH- species restricts its further development. Herein, the CuO-PdO heterogeneous interface is successfully constructed, resulting in an advanced onset-potential of the HMF oxidation reaction (HMFOR), a higher current density than CuO. The results of open-circuit potential, in situ infrared spectroscopy, and theoretical calculations indicate that the introduction of PdO enhances the adsorption capacity of the organic molecule. Meanwhile, the CuO-PdO heterogeneous interface promotes the adsorption and activation of OH- species, as demonstrated by zeta potential and electrochemical measurements. This work elucidates the adsorption enhancement mechanism of heterogeneous interfaces and provides constructive guidance for designing efficient multicomponent electrocatalysts in organic electrocatalytic reactions.

Super-strong CNT composite yarn with tight CNT packing via a compress-stretch process.

Carbon nanotube yarn (CNTY) with a large size and excellent mechanical properties could have wide technological influence in fields ranging from electrical devices to wearable textiles; however, inventing such CNTY has remained excessively challenging. Herein, we introduce an interesting approach to produce highly densified, robust CNT/polyvinyl alcohol composite yarn (CNT/PVA-P CY) with a large diameter and excellent comprehensive properties via a compressing and stretching method. Our method allows the PVA polymer chains to be well-dispersed into CNT intra- and inner-bundles with a controllable diameter and desirable mechanical properties. The resulting CNT/PVA-P CY exhibits an ultra-large diameter (∼140 µm), admirable mechanical properties (tensile strength of up to 1475 MPa and Young's modulus of up to 24.98 GPa), light weight (1.28 g cm-3), high electrical conductivity (792 S cm-1), outstanding flexibility, and anti-abrasive abilities. The successful obtainment of such attractive properties in yarns may provide new insights for the construction and exploitation of CNTY as a potential candidate to replace traditional carbon fibers for various applications.

Oxygen Vacancy-Mediated Selective C-N Coupling toward Electrocatalytic Urea Synthesis.

The electrocatalytic C-N coupling for one-step urea synthesis under ambient conditions serves as the promising alternative to the traditional urea synthetic protocol. However, the hydrogenation of intermediate species hinders the efficient urea synthesis. Herein, the oxygen vacancy-enriched CeO2 was demonstrated as the efficient electrocatalyst with the stabilization of the crucial intermediate of *NO via inserting into vacant sites, which is conducive to the subsequent C-N coupling process rather than protonation, whereas the poor selectivity of C-N coupling with protonation was observed on the vacancy-deficient catalyst. The oxygen vacancy-mediated selective C-N coupling was distinguished and validated by the in situ sum frequency generation spectroscopy. The introduction of oxygen vacancies tailors the common catalyst carrier into an efficient electrocatalyst with a high urea yield rate of 943.6 mg h-1 g-1, superior than that of partial noble-metal-based electrocatalysts. This work provides novel insights into the catalyst design and developments of coupling systems.

Distribution of Diatoms in the Navigable Sections of Beijing-Hangzhou Grand Canal.

OBJECTIVES: To establish a diatom database by analyzing the quatity, species distribution and differences of diatom in water samples of the whole navigable sections of the Beijing-Hangzhou Grand Canal, to provide a reference for the inference of the drowning site. METHODS: Water samples were collected at 22 sites in the navigable sections of the Beijing-Hangzhou Grand Canal (Jining section to Yangzhou Section), and the diatoms at each site were qualitatively and quantitatively analyzed by using graphite digestion-scanning electron microscopy. RESULTS: Sampling site T (Laohuaijiang River Line, Gaoyou City, Yangzhou City, Jiangsu Province) had the highest number of diatoms, while sampling site O (Siyang County, Suqian City, Jiangsu Province) had the lowest number of diatoms, with a large gap of 68 times. At sampling site Q (Jiangpu District, Huaian city, Jiangsu Province), there were 19 species of diatoms. The sampling site O had the least diatoms, with 7 species. There were no significant differences in species evenness and species diversity at each sampling site (P>0.05). Some sampling sites have characterized diatoms, such as Caloneis at station A (Taibai Lake, Weishan County, Shandong Province), Rhoicosphenia at station B (Nanyang Town, Weishan County, Shandong Province), Amphora at station I (Taierzhuang District, Zaozhuang City, Shandong Province) and Epithemia at station J (Pizhou 310 national highway, Xuzhou City, Jiangsu Province). CONCLUSIONS: The species richness of diatoms gradually increased from north to south. Diatom species richness and species diversity might be higher in areas with complex environments and large population flow. Climate type has a certain influence on the distribution of diatoms.