East China University of Technology

The presence of heavy metals in the industrial effluents has recently been a challenging issue for human health. Efficient removal of heavy metal ions from environment is one of the most important issues from biological and environmental point of view, and many studies have been devoted to investigate the environmental behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic heavy metal ions, present both in the surface and underground wastewater. The aim of this review is to show the excellent removal capacity and environmental remediation of NZVI-based materials for various heavy metal ions. A new look on NZVI-based materials (e.g., modified or matrix-supported NZVI materials) and possible interaction mechanism (e.g., adsorption, reduction and oxidation) and the latest environmental application. The effects of various environmental conditions (e.g., pH, temperature, coexisting oxy-anions and cations) and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and potential areas for future applications in environment remediation are also proposed.

This edition contains papers dedicated on research results that were presented at the 12th Annual International Conference on Material Science and Engineering (ICMSE 2024, 26-28 July 2024, Hangzhou, Zhejiang, China) that emphasis a broad spectrum of issues and solutions related to mechanical engineering - design machines, tools and equipment; reliability and durability of engineering structures, big data and applications of artificial intelligence, engineering management and ecological safety. The publication will be helpful for many specialists in machinery, information technologies, production organisation and environmental engineering.

As a new enterprise development model, digitization is of great significance to the development of economy and society. Using the data of relevant listed companies from 2012 to 2020, the panel measurement model is used to investigate the relationship between digital transformation and enterprise performance to further reveal the internal law of whether digital transformation helps to stimulate innovation momentum. The results show that digital transformation has greatly improved the performance of enterprises, and it can stimulate the momentum of enterprise innovation. Reducing costs, increasing revenue, improving efficiency, and encouraging innovation are the main paths for digital transformation to enable the development of enterprises, among which the policy effect of enterprise innovation is the most significant. This research is of great significance to improve the user demand orientation of enterprise innovation and research and development, as well as to realize the high-quality innovation and development of enterprises.

A new metal-organic framework Zn2(H2O)(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the well-established MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn(2+) sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm(3)/cm(3)) to Zn-MOF-74. Interestingly, the accessible Zn(2+) sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm(3)/cm(3)) than Zn-MOF-74 (146 cm(3)/cm(3)) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result.

Amine grafting on MOFs greatly enhances the adsorbability of Cr-MIL-101 towards U(<sc>vi</sc>) from an aqueous solution, and the enhancement depends on the coverage and flexibility of the grafted amino group.

Curcumin is a multifunctional and natural agent considered to be pharmacologically safe. However, its application in the food and medical industry is greatly limited by its poor water solubility, physicochemical instability and inadequate bioavailability. Nanoliposome encapsulation could significantly enhance the solubility and stability of curcumin. Curcumin nanoliposomes exhibited good physicochemical properties (entrapment efficiency = 57.1, particle size = 68.1 nm, polydispersity index = 0.246, and zeta potential = -3.16 mV). Compared with free curcumin, curcumin nanoliposomes exhibited good stability against alkaline pH and metal ions as well as good storage stability at 4 °C. Curcumin nanoliposomes also showed good sustained release properties. Compared with free curcumin, curcumin nanoliposomes presented an equal cellular antioxidant activity, which is mainly attributed to its lower cellular uptake as detected by fluorescence microscopy and flow cytometry. This study provide theoretical and practical guides for the further application of curcumin nanoliposomes.

Abstract Tuning surface electron transfer process by oxygen (O)‐vacancy engineering is an efficient strategy to develop enhanced catalysts for CO 2 electroreduction (CO 2 ER). Herein, a series of distinct InO x NRs with different numbers of O‐vacancies, namely, pristine (P‐InO x ), low vacancy (O‐InO x ) and high‐vacancy (H‐InO x ) NRs, have been prepared by simple thermal treatments. The H‐InO x NRs show enhanced performance with a best formic acid (HCOOH) selectivity of up to 91.7 % as well as high HCOOH partial current density over a wide range of potentials, largely outperforming those of the P‐InO x and O‐InO x NRs. The H‐InO x NRs are more durable and have a limited activity decay after continuous operating for more than 20 h. The improved performance is attributable to the abundant O‐vacancies in the amorphous H‐InO x NRs, which optimizes CO 2 adsorption/activation and facilitates electron transfer for efficient CO 2 ER.

Abstract An ideal porous adsorbent toward uranium with not only large adsorption capacity and high selectivity but also broad applicability even under rigorous conditions is highly desirable but still extremely scarce. In this work, a porous adsorbent, namely [NH 4 ] + [COF‐SO 3 − ], prepared by ammoniating a SO 3 H‐decorated covalent organic framework (COF) enables remarkable performance for uranium extraction. Relative to the pristine SO 3 H‐decorated COF (COF‐SO 3 H) with uranium adsorption capacity of 360 mg g −1 , the ammoniated counterpart of [NH 4 ] + [COF‐SO 3 − ] affords ultrahigh uranium uptake up to 851 mg g −1 , creating a 2.4‐fold enhancement. Such a value is the highest among all reported porous adsorbents for uranium. Most importantly, a large distribution coefficient, K d U , up to 9.8 × 10 6 mL g −1 is observed, implying extremely strong affinity toward uranium. Consequently, [NH 4 ] + [COF‐SO 3 − ] affords highly selective adsorption of uranium over a broad range of metal ions such as S U/Cs = 821, S U/Na = 277, and S U/Sr = 124, making it as effective uranium adsorbent from seawater, resulting in amazing uranium adsorption capacity of 17.8 mg g −1 . Moreover, its excellent chemostability also make it an effective uranium adsorbent even under rigorous conditions (pH = 1, 8, and 3 m acidity).

Most porphyry Cu deposits in the world occur in magmatic arc settings and are formed in association with calc-alkaline arc magmas related to subduction of oceanic lithosphere. This contribution reviews a number of significant porphyry Cu deposits in the eastern Tethyan metallogenic domain. They widely occur in a variety of non-arc settings, varying from post (late)-collisional transpressional and extensional environments to intracontinental extensional environments related to orogenic and anorogenic processes. Their spatial–temporal localization is controlled by strike–slip faults, orogen-transverse normal faults, lineaments and their intersections in these non-arc settings. These deposits are dominated by porphyry Cu–Mo deposits with minor porphyry Cu–Au and epithermal Au deposits, and exhibit a broad similarity with those in magmatic arcs. The associated magmas are generally hydrous, relatively high fO2, high-K calc-alkaline and shoshonitic, and show geochemical affinity with adakites. They are distinguished from arc magmas and/or oceanic-slab derived adakites, by their occurrence as isolated complexes, high K2O contents (1.2–8.5%), and much wider range of εNd(t) values(− 10 to + 3) and positive εHf(t) values (+ 4.6 to + 6.9). These potassic magmas are most likely formed by partial melting of thickened juvenile mafic lower-crust or delaminated lower crust, but also involving various amounts of asthenospheric mantle components. Key factors that generate hydrous fertile magmas are most likely crust/mantle interaction processes at the base of thickened lower-crust in non-arc settings, rather than oceanic-slab dehydration (as in arc settings). Breakdown of amphibole in thickened lower crust (e.g., amphibole eclogite and garnet amphibolite) during melting is considered to release fluids into the fertile magmas, leading to an elevated oxidation state and higher H2O content necessary for development of porphyry Cu–Mo–Au systems. Copper and Au in hydrous magmas are likely derived from mantle-derived components and/or melts, which either previously underplated and infiltrated at the base of the thickened lower crust, or were input into the primitive magmas by melt/mantle interaction. In contrast, Mo and (part of the) S in the fertile magmas are probably supplied by old crust during melting and subsequent ascent.

Abstract The mass balance in the Inner Tibet Plateau (ITP) derived from the Gravity Recovery and Climate Experiment (GRACE) showed a positive rate that was attributed to the glacier mass gain, whereas glaciers in the region, from other field‐based studies, showed an overall mass loss. In this study, we examine lake's water level and mass changes in the Tibetan Plateau (TP) and suggest that the increased mass measured by GRACE was predominately due to the increased water mass in lakes. For the 200 lakes in the TP with 4 to 7 years of ICESat data available, the mean lake level and total mass change rates were +0.14 m/yr and +4.95 Gt/yr, respectively. Compared those in the TP, 118 lakes in the ITP showed higher change rates (+0.20 m/yr and +4.28 Gt/yr), accounting for 59% area and 86% mass increase of the 200 lakes. The lake's mass increase rate in the ITP explains the 61% increased mass (~7 Gt/yr) derived from GRACE [ Jacob et al ., 2012], while it only accounts for 53% of the total lake area in the ITP.

Graphene oxide (GO) has attracted considerable attention because of its remarkable enhanced adsorption and multifunctional properties. However, the toxic properties of GO nanosheets released into the environment could lead to the instability of biological system. In aqueous phase, GO may interact with fine mineral particles, such as chloridion intercalated nanocrystallined Mg/Al layered double hydroxides (LDH-Cl) and nanocrystallined Mg/Al LDHs (LDH-CO3), which are considered as coagulant molecules for the coagulation and removal of GO from aqueous solutions. Herein the coagulation of GO on LDHs were studied as a function of solution pH, ionic strength, contact time, temperature and coagulant concentration. The presence of LDH-Cl and LDH-CO3 improved the coagulation of GO in solution efficiently, which was mainly attributed to the surface oxygen-containing functional groups of LDH-Cl and LDH-CO3 occupying the binding sites of GO. The coagulation of GO by LDH-Cl and LDH-CO3 was strongly dependent on pH and ionic strength. Results of theoretical DFT calculations indicated that the coagulation of GO on LDHs was energetically favored by electrostatic interactions and hydrogen bonds, which was further evidenced by FTIR and XPS analysis. By integrating the experimental results, it was clear that LDH-Cl could be potentially used as a cost-effective coagulant for the elimination of GO from aqueous solutions, which could efficiently decrease the potential toxicity of GO in the natural environment.

Abstract Separation of C 2 H 4 from C 2 H 4 /C 2 H 2 /C 2 H 6 mixture with high working capacity is still a challenging task. Herein, we deliberately design a Th-metal-organic framework (MOF) for highly efficient separation of C 2 H 4 from a binary C 2 H 6 /C 2 H 4 and ternary C 2 H 4 /C 2 H 2 /C 2 H 6 mixture. The synthesized MOF Azole-Th-1 shows a UiO-66-type structure with fcu topology built on a Th 6 secondary building unit and a tetrazole-based linker. Such noticeable structure, is connected by a N,O-donor ligand with high chemical stability. At 100 kPa and 298 K Azole-Th-1 performs excellent separation of C 2 H 4 (purity &gt; 99.9%) from not only a binary C 2 H 6 /C 2 H 4 (1:9, v/v) mixture but also a ternary mixture of C 2 H 6 /C 2 H 2 /C 2 H 4 (9:1:90, v/v/v), and the corresponding working capacity can reach up to 1.13 and 1.34 mmol g −1 , respectively. The separation mechanism, as unveiled by the density functional theory calculation, is due to a stronger van der Waals interaction between ethane and the MOF skeleton.

Rational control of the interlayer space of multilayered Ti₃C₂T_xenables the MXene to exhibit an excellent U(<sc>vi</sc>) sorption capacity and an exceptional radionuclide encapsulation performance.

The development of nonprecious-metal-based electrocatalysts with high oxygen reduction reaction (ORR) activity, low cost, and good durability in both alkaline and acidic media is very important for application of full cells. Herein, we developed a facile and economical strategy to obtain porous core-shell Fe3C embedded nitrogen-doped carbon nanofibers (Fe3C@NCNF-X, where X denotes pyrolysis temperature) by electrospinning of polyvinylidene fluoride (PVDF) and FeCl3 mixture, chemical vapor phase polymerization of pyrrole, and followed by pyrolysis of composite nanofibers at high temperatures. Note that the FeCl3 and polypyrrole acts as precursor for Fe3C core and N-doped carbon shell, respectively. Moreover, PVDF not only plays a role as carbon resources, but also provides porous structures due to hydrogen fluoride exposure originated from thermal decomposition of PVDF. The resultant Fe3C@NCNF-X catalysts, particularly Fe3C@NCNF-900, showed efficient electrocatalytic performance for ORR in both alkaline and acidic solutions, which are attributed to the synergistic effect between Fe3C and N-doped carbon as catalytic active sites, and carbon shell protects Fe3C from leaching out. In addition, the Fe3C@NCNF-X catalyst displayed a better long-term stability, free from methanol crossover and CO-poisoning effects than those of Pt/C, which is of great significance for the design and development of advanced electrocatalysts based on nonprecious metals.

How to optimize the enzyme-like catalytic activity of nanozymes to improve their applicability has become a great challenge. Herein, we present an l-cysteine (l-Cys) coordination-driven self-assembly strategy to activate polyvinylpyrrolidone (PVP)-modified Cu single-atom nanozymes MoOx-Cu-Cys (denoted as MCCP SAzymes) aiming at catalytic tumor-specific therapy. The Cu single atom content of MCCP can be rationally modulated to 10.10 wt %, which activates the catalase (CAT)-like activity of MoOx nanoparticles to catalyze the decomposition of H2O2 in acidic microenvironments to increase O2 production. Excitingly, the maximized CAT-like catalytic efficiency of MCCP is 138-fold higher than that of typical MnO2 nanozymes and exhibits 14.3-fold higher affinity than natural catalase, as demonstrated by steady-state kinetics. We verify that the well-defined l-Cys-Cu···O active sites optimize CAT-like activity to match the active sites of natural catalase through an l-Cys bridge-accelerated electron transfer from Cys-Cu to MoOx disclosed by density functional theory calculations. Simultaneously, the high loading Cu single atoms in MCCP also enable generation of •OH via a Fenton-like reaction. Moreover, under X-ray irradiation, MCCP converts O2 to 1O2 for cascading radiodynamic therapy, thereby facilitating the multiple reactive oxygen species (ROS) for radiosensitization to achieve substantial antitumor.

Novel rod-like ternary nanoscale layered double hydroxides (Ca-Mg-Al-LDH) and their bimetal derivatives (Ca-Mg-Al-LDOx, x: 200, 300, 400, 500, and 600 °C) were fabricated with a simple-green hydrothermal and calicination process. The interaction mechanism and adsorption property of U(VI) on Ca-Mg-Al-LDH and Ca-Mg-Al-LDOx were investigated by a batch technique and spectroscopy analysis, and the results indicated that U(VI) could form strong and stable surface complexes on Ca-Mg-Al-LDH and Ca-Mg-Al-LDOx surfaces. The adsorption capacity of U(VI) on various adsorbents could be controlled and adjusted through changing the calcination temperature, which was attributed to the different contents of various metal–oxide bonds (e.g., Ca–O, Mg–O, and Al–O). The adsorption capacities of U(VI) on these adsorbents were in the order of Ca-Mg-Al-LDO500 (486.8 mg/g) > Ca-Mg-Al-LDO600 (373.4 mg/g) > Ca-Mg-Al-LDO400 (292.5 mg/g) > Ca-Mg-Al-LDO300 (260.0 mg/g) > Ca-Mg-Al-LDO200 (223.5 mg/g) > Ca-Mg-Al-LDH (132.5 mg/g), which might be attributed to more active surface sites and abundant “Ca–O and Al–O” with the increase of calcination temperature. The results of kinetic and thermodynamic studies demonstrated that the adsorption was a spontaneous and endothermic chemical process, and the better fitted Sips model revealed that the adsorption reaction was multilayer adsorption at low concentration of U(VI) and monolayer adsorption at high concentration of U(VI). This study provided highlights on the interaction mechanism of U(VI) with various metal–oxide bonds, and it could play an important role for the controllable adsorption capacity and effcient application in environmental remediation.

Anthropogenic activities in coastal regions are endangering marine ecosystems. Coastal waters classified as case-II waters are especially complex due to the presence of different constituents. Recent advances in remote sensing technology have enabled to capture the spatiotemporal variability of the constituents in coastal waters. The present study evaluates the potential of remote sensing using machine learning techniques, for improving water quality estimation over the coastal waters of Hong Kong. Concentrations of suspended solids (SS), chlorophyll-a (Chl-a), and turbidity were estimated with several machine learning techniques including Artificial Neural Network (ANN), Random Forest (RF), Cubist regression (CB), and Support Vector Regression (SVR). Landsat (5,7,8) reflectance data were compared with in situ reflectance data to evaluate the performance of machine learning models. The highest accuracies of the water quality indicators were achieved by ANN for both, in situ reflectance data (89%-Chl-a, 93%-SS, and 82%-turbidity) and satellite data (91%-Chl-a, 92%-SS, and 85%-turbidity. The water quality parameters retrieved by the ANN model was further compared to those retrieved by “standard Case-2 Regional/Coast Colour” (C2RCC) processing chain model C2RCC-Nets. The root mean square errors (RMSEs) for estimating SS and Chl-a were 3.3 mg/L and 2.7 µg/L, respectively, using ANN, whereas RMSEs were 12.7 mg/L and 12.9 µg/L for suspended particulate matter (SPM) and Chl-a concentrations, respectively, when C2RCC was applied on Landsat-8 data. Relative variable importance was also conducted to investigate the consistency between in situ reflectance data and satellite data, and results show that both datasets are similar. The red band (wavelength ≈ 0.665 µm) and the product of red and green band (wavelength ≈ 0.560 µm) were influential inputs in both reflectance data sets for estimating SS and turbidity, and the ratio between red and blue band (wavelength ≈ 0.490 µm) as well as the ratio between infrared (wavelength ≈ 0.865 µm) and blue band and green band proved to be more useful for the estimation of Chl-a concentration, due to their sensitivity to high turbidity in the coastal waters. The results indicate that the NN based machine learning approaches perform better and, thus, can be used for improved water quality monitoring with satellite data in optically complex coastal waters.

The enhanced interaction of β-cyclodextrin modified graphitic carbon nitride (g-C₃N₄/β-CD) or g-C₃N₄ with methyl orange (MO) or Pb(<sc>ii</sc>) in natural environmental remediation.

Electrospray ionization (ESI) is a mass spectrometric technique widely used in various fields including chemistry, biology, medicine, pharmaceutical industry, clinical assessment, and forensic science. In this study, we report a simple and economical ESI-mass spectrometry (MS) technique, which makes use of disposable wooden tips (wooden toothpicks) for loading and ionization of samples. Samples could be loaded by normal pipetting onto the tip or simply dipping the tip into sample solutions. The hydrophilic and porous nature of wood allows effective adhesion of the sample solution for durable ion signals. The tip can be directly connected to nano-ESI ion sources of various mass spectrometers. Upon application of high voltage to the tip, desirable mass spectra could be obtained. We demostrated that this new technique is applicable for analysis of various samples, including organic compounds, organometallic compounds, peptides, proteins, and samples that cannot be directly analyzed by conventional ESI techniques, e.g., slurry samples and powder samples. The slim and hard properties of the wooden tip enable sampling from specific locations such as corners and small openings, indicating potential applications of the new technique in forensic investigations. The observation of electrospray ionization from wooden materials also allows us to get new insights into the materials that can be directly ionized for mass spectrometric analysis.

Abstract Temperature changes over the Tibetan Plateau (TP) exhibit a dependence on altitude, as observed from meteorological station data and Moderate Resolution Imaging Spectroradiometer (MODIS) land surface temperature (LST) data. However, little is known about the changes in water surface temperature (WST) of lakes in the TP under the warming climate conditions over the past few decades. In this study, lake WST was examined using a MODIS/Terra 8 day LST (nighttime) product (MOD11A2) over the period 2001–2012. It was found that 52 lakes included in the analysis of WST exhibited an average rate of change of 0.012 ± 0.033°C/yr. Of these 52 lakes, 31 lakes (60%) displayed a temperature increase with a mean warming rate of 0.055 ± 0.033°C/yr and 21 lakes (40%) displayed a temperature decrease with a mean cooling rate of −0.053 ± 0.038°C/yr. The rates of change in WST for 13 lakes were statistically significant, and these included nine warming and four cooling lakes. Of the 17 lakes with nearby weather stations, nine lakes (53%) showed faster warming than nearby air/land. The warming lakes could be attributed to locally rising air and land surface temperatures as well as other factors such as the decreased lake ice cover. The cooling lakes were mostly located at high elevations (&gt;4200 m), and the trend could have been due to increased cold water discharge to the lakes from accelerated glacier/snow melts. Therefore, both warming and cooling lake temperatures in the TP were possibly the result of increased air temperatures (0.036 ± 0.027°C/yr) under global warming conditions.