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The significance of resource recycling for coking wastewater treatment:based on environmental and economic life cycle assessment

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Green Chemical Engineering 2024年第1期5卷 50-59页

作者： Di Zhang He Zhao Wenfang Gao Yuxing Sheng Hongbin Cao Institute of Process Engineering Innovation Academy for Green ManufactureChinese Academy of SciencesBeijing100190China University of Chinese Academy of Sciences Beijing100049China Chemistry&Chemical Engineering Data Center Chinese Academy of SciencesBeijing100190China Tianjin key laboratory of Clean Energy and Pollutant Control School of Energy and Environmental EngineeringHebei University of TechnologyTianjin300401China

The sustainability of the coking industry is supported by reasonable production profit and environmental quality requirements.The traditional measures substantially increased the related costs for enterprises to reach standards.This paper aims to develop a comprehensive cost combined environmental impact assessment method that is necessary for the analysis of wastewater treatment systems.Typical three coking wastewater treatment processes in China were evaluated.Results showed that eutrophication dominantly contributed to the overall environmental effect.Improving effluent quality could significantly reduce the total environmental impact.In terms of an economic perspective,the price of raw materials was the main factor that affected the operating cost of comprehensive treatment.Based on subsystem analysis,the pretreatment stage accounted for the majority of environmental and cost burdens,respectively reaching 64%-78%and 64%-86%.Optimizing the pretreatment process by enhancing the efficiency of high concentration raw material recovery and substituting toxic raw materials for extractant could reduce the environmental impact and economic cost by 43.8%and 57%,respectively,which was an effective way to improve the potential performance of coking wastewater treatment plants(WWTPs).

关键词： Life cycle assessment Environmental impact Economic evaluation Coking wastewater treatment Resource recycling Comprehensive benefits

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Formation and transformation of metastable LPSO building blocks clusters in Mg-Gd-Y-Zn-Zr alloys by spinodal decomposition and heterogeneous nucleation

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Journal of Magnesium and Alloys 2024年第2期12卷 673-686页

作者： Xin Zhao Zhong Yang Jiachen Zhang Minxian Liang Liying Wang School of materials Science and Chemical Engineering Xi’an Technological UniversityXi’an 710021China Xi’an Tianli Metal Composite Material Co.Ltd. Xi’an 710299China

To study the formation and transformation mechanism of long-period stacked ordered(LPSO)structures,a systematic atomic scale analysis was conducted for the structural evolution of long-period stacked ordered(LPSO)structures in the Mg-Gd-Y-Zn-Zr alloy annealed at 300℃~500℃.Various types of metastable LPSO building block clusters were found to exist in alloy structures at different temperatures,which precipitate during the solidification and homogenization process.The stability of Zn/Y clusters is explained by the first principles of density functional theory.The LPSO structure is distinguished by the arrangement of its different Zn/Y enriched LPSO structural units,which comprises local fcc stacking sequences upon a tightly packed plane.The presence of solute atoms causes local lattice distortion,thereby enabling the rearrangement of Mg atoms in the different configurations in the local lattice,and local HCP-FCC transitions occur between Mg and Zn atoms occupying the nearest neighbor positions.This finding indicates that LPSO structures can generate necessary Schockley partial dislocations on specific slip surfaces,providing direct evidence of the transition from 18R to 14H.Growth of the LPSO,devoid of any defects and non-coherent interfaces,was observed separately from other precipitated phases.As a result,the precipitation sequence of LPSO in the solidification stage was as follows:Zn/Ycluster+Mg layers→various metastable LPSO building block clusters→18R/24R LPSO;whereas the precipitation sequence of LPSO during homogenization treatment was observed to be as follows:18R LPSO→various metastable LPSO building block clusters→14H LPSO.Of these,14H LPSO was found to be the most thermodynamically stable structure.

关键词： LPSO Spinodal decomposition Homogenization treatment Clusters Phase transformation

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Stabilization/solidification mechanisms of tin tailings and fuming slag-based geopolymers for different heavy metals

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Frontiers of Environmental Science & Engineering 2024年第5期18卷 43-55页

作者： Xian Zhou Zhengfu Zhang Hui Yang School of materials Science and Engineering Kunming University of Science and TechnologyKunming650093China Kunming Metallurgical Research Institute Co. Ltd.Kunming650031China

Tin mine tailings(TMT)and fuming slag(FS)contain many heavy metals(As,Cr,Cu,Zn and Mn)that cause severe pollution to the environment.Herein,geopolymers were prepared using TMT,FS and flue gas desulfurization gypsum(FGDG)to immobilize heavy metals,and their compressive strength and heavy metal leaching toxicity were investigated.It was first determined that T4F5(TMT:FS=4:5)sample exhibited the highest compressive strength(7.83 MPa).T4F5 achieved 95%immobilization efficiency for As and Cr,and nearly 100%for Cu,Zn and Mn,showing good immobilization performance.A series of characterization analyses showed that heavy metal cations can balance the charge in the geopolymer and replace Al in the geopolymer structure to form covalent bonds.In addition,about 2%–20%of heavy metal Fe was immobilized in hydration products,heavy metal hydroxides and non-bridging Si–O and Al–O coordination with silica-aluminate matrices.AsO33−was oxidized into AsO43−,which may form Ca–As or Fe–As precipitates.Cr2O72−was converted to CrO42−under alkaline environment and then combined with OH−to form Cr(OH)3 precipitates.Mn2+may react directly with dissolved silicate to form Mn2SiO4 and also form Mn(OH)2 precipitates.The unstable Mn(OH)2 can be further oxidized to MnO2.The heavy metal cations were immobilized in the silicoaluminate lattice,while the anions tended to form insoluble precipitates.These results may benefit the industry and government for better handling of TMT,FS and solid wastes containing the abovementioned five heavy metals.

关键词： Heavy metals Cementitious materials Tin tailings Stabilization/solidification Redox

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Polythiophene solar cells processed from non-halogenated solvent with 15.68%efficiency

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Science China Chemistry 2023年第8期66卷 2347-2353页

作者： Xiaoxin Tan Youle Li Xiyue Yuan Seoyoung Kim Yue Zhang Changduk Yang Fei Huang Yong Cao Chunhui Duan Institute of Polymer Optoelectronic materials and devices State Key Laboratory of Luminescent Materials and DevicesSouth China University of TechnologyGuangzhou510640China School of Energy and Chemical Engineering Perovtronics Research CenterLow Dimensional Carbon Materials CenterUlsan National Institute of Science and Technology(UNIST)Ulsan44919Republic of Korea

Polythiophenes(PTs)are prospective polymer donors for large-scale manufacturing and industrialization owing to their simple structures and low synthetic cost.However,the fabrication of PT solar cells depends on highly toxic chlorinated solvents,and less research has been done on the use of more environmentally friendly non-halogenated solvents.Herein,highly efficient PT solar cells based on top-performance polythiophene,P5TCN-F25,processed from a non-halogenated solvent are reported by delicate aggregation control.A power conversion efficiency of up to 15.68%was achieved by depositing the active layer from a hot o-xylene solution,which is the record efficiency of non-halogenated processed PT solar cells up to date.The appropriate solution temperature is beneficial to the formation of ordered polymer stacking and desirable phase separation size,which thereby contributes to enhanced charge transfer efficiency,more balanced hole/electron mobility,and reduced trap-assisted recombination.These results provide valuable implications for improving the efficiency of PT solar cells via environmentallyfriendly processing.

关键词： polythiophenes organic solar cells high-efficiency non-halogenated solvent aggregation control

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A General Authentication and key Agreement Framework for Industrial Control System

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Chinese Journal of Electronics 2024年第4期33卷 1046-1062页

作者： Shan GAO Junjie CHEN Bingsheng ZHANG Kui REN Xiaohua YE Yongsheng SHEN School of Cyber Science and Technology Zhejiang University Hangzhou Global Scientific and Technological Innovation Center Zhejiang University Zhejiang Provincial key laboratory of Blockchain and Cyberspace Governance Hangzhou City Brain Co. Ltd

In modern industrial control systems(ICSs), when user retrieving the data stored in field device like smart sensor, there exists two main problems: one is lack of the verification for identification of user and field device;the other is that user and field device need exchange a key to encrypt sensitive data transmitted over the network.We propose a comprehensive authentication and key agreement framework that enables all connected devices in an ICS to mutually authenticate each other and establish a peer-to-peer session key. The framework combines two types of protocols for authentication and session key agreement: The first one is an asymmetric cryptographic key agreement protocol based on transport layer security handshake protocol used for Internet access, while the second one is a newly designed lightweight symmetric cryptographic key agreement protocol specifically for field devices. This proposed lightweight protocol imposes very light computational load and merely employs simple operations like one-way hash function and exclusive-or(XOR) operation. In comparison to other lightweight protocols, our protocol requires the field device to perform fewer computational operations during the authentication phase. The simulation results obtained using Open SSL demonstrates that each authentication and key agreement process in the lightweight protocol requires only 0.005 ms. Our lightweight key agreement protocol satisfies several essential security features, including session key secrecy, identity anonymity, untraceability, integrity, forward secrecy, and mutual authentication. It is capable of resisting impersonation, man-in-the-middle, and replay attacks. We have employed the Gong-NeedhamYahalom(GNY) logic and automated validation of Internet security protocols and application tool to verify the security of our symmetric cryptographic key agreement protocol.

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Nanostructured bimetallic Zn/Co in N-doped carbon as an efficient catalyst for the alcohol dehydrogenation to carboxylic acids under solvent-free conditions

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Journal of materials Science & Technology 2023年第30期161卷 111-122页

作者： Zhong-Hui Zheng Somboon Chaemchuen Jun-Fei Gu Jing Hang Wei Sang Ji-Chao Wang Ye Yuan Cheng Chen State key laboratory of advanced Technology for materials Synthesis and Processing Wuhan University of TechnologyWuhan 430070China School of materials Science and Engineering Wuhan University of TechnologyWuhan 430070China

The catalytic alcohol dehydrogenation to carboxylic acids has been demonstrated as an atom-economic and environmental-friendly synthetic method.However,the reported catalysts either require relatively complicated synthesis or exhibit high activity only in the presence of a solvent.Therefore,it is still in high demand to obtain catalysts that feature facile synthesis and perform well even without any solvent.Herein,a series of nanostructured bimetallic Zn/Co species embedded in N-doped hierarchical porous carbon were fabricated in a facile and green manner.More significantly,the best-performing material(Zn/Co@NC-800)was identified as the first heterogeneous catalyst to enable this transformation under solvent-free conditions.Moreover,the as-prepared composites were comprehensively investigated to de-termine their structural and morphological properties,which rationalized the superiority of Zn/Co@NC-800 over the other synthesized materials.Further studies signified that Co sites(both Co^(0)and Co^(2+))and N species(mainly pyridinic N)were probably involved in this process,functioning as the Lewis acid site and basic site,respectively.Hopefully,this study could provide a simple and sustainable method for carboxylic acid synthesis.

关键词： Heterogeneous catalysis Bimetallic ZIFs Pyrolysis Solvent-free Alcohol dehydrogenation Carboxylic acids

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Improving the stability and scalability of all-inorganic inverted CsPbI_(2)Br perovskite solar cell

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Journal of Energy Chemistry 2022年第5期31卷 176-183页

作者： Chenghao Duan Qiaoyun Wen Yan Fan Jiong Li Zidan Liu keyou Yan School of Environment and Energy State Key Laboratory of Luminescent Materials and DevicesGuangdong Provincial Key Laboratory of Solid Wastes Pollution Control and RecyclingSouth China University of TechnologyGuangzhou 510000GuangdongChina Medical devices Research&Testing Center South China University of TechnologyGuangzhou 510000GuangdongChina

All-inorganic perovskite solar cells(PSCs) have potential to pass the stability international standard of IEC61215:2016 but cannot deliver high performance and stability due to the poor interface contact. In this paper, Sn-doped TiO_(2)(Ti_(1-x)Sn_(x)O_(2)) ultrathin nanoparticles are prepared for electron transport layer(ETL) by solution process. The ultrathin Ti_(1-x)Sn_(x)O_(2) nanocrystals have greatly improved interface contact due to the facile film formation, good conductivity and high work function. The all-inorganic inverted NiOx/CsPbI_(2)Br/Ti_(1-x)Sn_(x)O_(2)p-i-n device shows a power conversion efficiency(PCE) of 14.0%. We tested the heat stability, light stability and light-heat stability. After stored in 85℃ for 65 days, the inverted PSCs still retains 98% of initial efficiency. Under continuous standard one-sun illumination for 600 h,there is no efficiency decay, and under continuous illumination at 85℃ for 200 h, the device still retains 85% of initial efficiency. The 1.0 cm^(2) device of inverted structure shows a PCE of up to 11.2%. The ultrathin Ti_(1-x)Sn_(x)O_(2)is promising to improve the scalability and stability and thus increase the commercial prospect.

关键词： All-inorganic perovskite Sn-doped TiO_(2) Ultrathin nanocrystal Stability Scalability

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Activating Inert Sites in Cobalt Silicate Hydroxides for Oxygen Evolution through Atomically Doping

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Energy & Environmental materials 2022年第2期5卷 655-661页

作者： Jiexin Zhu Lixue Xia Wenxuan Yang Ruohan Yu Wei Zhang Wen Luo Yuhang Dai Wei Wei Liang Zhou Yan Zhao Liqiang Mai State key laboratory of advanced Technology for materials Synthesis and Processing Wuhan University of TechnologyWuhan 430070China International School of materials Science and Engineering Wuhan University of TechnologyWuhan 430070China Foshan Xianhu laboratory of the advanced Energy Science and Technology Guangdong laboratory Xianhu Hydrogen ValleyFoshan 528200China

Metal silicate hydroxides have been recognized as efficient oxygen evolution reaction(OER)electrocatalysts,yet tailoring of their intrinsic activity remains confused.Herein,Fe had been incorporated into cobalt silicate hydroxide nanosheets and the resulted material achieves a competitive OER catalytic activity.It is found that the doping state obviously affects the electrical transport property.Specifically,highly dispersed Fe atoms(low-concentration Fe doping)trigger slight electron transfer to Co atoms while serried Fe(highconcentration Fe doping)attract vast electrons.By introducing 6 at.%Fe doping,partial relatively inert Co sites are activated by atomically dispersed Fe,bearing an optimal metal 3d electronic occupation and adsorption capacity to oxygen intermediate.The introduced Co-O-Fe unit trigger the p-donation effect and decrease the number of electrons in p*-antibonding orbitals,which enhance the Fe-O covalency and the structural stability.As a result,the sample delivers a low overpotential of 293 mV to achieve a current density of 10 mA cm^(-2).This work clarifies the superiority of atomically dispersed doping state,which is of fundamental interest to the design of doped catalyst.

关键词： atomically doping electrochemistry electron transfer metal silicate hydroxides oxygen evolution

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Quantitative reorientation behaviors of macro-twin interfaces in shape-memory alloy under compression stimulus in situ TEM

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Journal of materials Science & Technology 2022年第12期107卷 243-251页

作者： Bin Chen Chaoshuai Guan Yong Li Chong Yang Junwei Zhang Gang Liu Lingwei Li Yong Peng School of materials and Energy Electron Microscopy Centre of Lanzhou University and Key Laboratory of Magnetism and Magnetic Materials of the Ministry of EducationLanzhou UniversityLanzhou 730000China key laboratory of Novel materials for Sensor of Zhejiang Province Institute of Advanced Magnetic MaterialsHangzhou Dianzi UniversityHangzhou 310012China School of materials Science and Engineering Xi’an Jiaotong UniversityXi’an 710000China

Twinning stress is known to be a critical factor for the actuating performance of magnetic shape memory alloys because of the harmful deterioration of their magnetic field-induced strain effect.However,the intrinsic origin of the high twinning stress is still in debate.In this work,we firstly fill this gap by precisely probing the reorientation behaviors of A-C and A-B two common macro-twin interfaces under the stimulus of uniaxial compression in-situ transmission electron microscope.The grain boundary is proved to be the main reason for large twinning stress.The twinning stress of the A-C and A-B type interfaces quantitatively are~0.69 and 1.27 MPa within the plate respectively.The A-C type interface evidently has smaller twinning stress and larger deformation variable than the A-B interface.Under the action of compression,not only the orientations of the crystals have changed,but also the roles of the major and minor lamellae have changed for both interfaces due to the movements of twinning dislocations.Combining insitu and quasi in-situ electron diffraction data,the reorientation process is clearly and intuitively shown by the stereographic projection.Atomic models and the theory of dislocation motion are proposed to phenomenologically clarify the intrinsic mechanism.This work is believed to not only provide a deeper understanding of the deformation mechanism of magnetic shape memory alloys under uniaxial compression testing,but also discover that compression training is not the mechanical training way to decrease the twinning stress of non-modulated martensite in single crystal shape memory alloys.

关键词： Magnetic shape memory alloys Non-modulated martensite Reorientation behavior Twinning stress In-situ TEM

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An isolation strategy to anchor atomic Ni or Co cocatalysts on TiO_(2)(A)for photocatalytic hydrogen production

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Nano Research 2022年第7期15卷 5848-5856页

作者： Shangchun Lv Mengxi Pei Yuxiang Liu Zhichun Si Xiaodong Wu Rui Ran Duan Weng Feiyu Kang International Graduate School at Shenzhen Tsinghua UniversityShenzhen 518055China The key laboratory of advanced materials of Ministry of Education School of Materials Science and EngineeringTsinghua UniversityBeijing 100084China

TiO_(2) has been considered as an ideal photocatalyst for water splitting.However,narrow light absorbance,low charge separation efficiency,and rare surface active sites lead to the low photocatalytic efficiency of TiO_(2).Although extensive research attempted to improve the situation,there is still lack of method for constructing high active and noble-metal-free TiO_(2) photocatalyst for H_(2) evolution reactions(HER).In this work,we loaded single atomic(SA)Ni(or Co)on the surface of anatase TiO_(2)(TiO_(2)(A))nanosheets by an isolation strategy.Ethylene diamine tetraacetic acid and ethylene glycol(EDTA-EG)compounds were used to chelate metal ions in solution and form carbon quantum dots in the following thermal treatment to isolate the metal ions on surface of TiO_(2)(A).The prepared Ni SA/TiO_(2)(A)catalyst owned a“skin wrapped body”structure with in-situ formed twodimensional(2D)heterojunction facilitating the fast electron transfer.As a result,the Ni SA/TiO_(2)(A)catalyst showed a high H_(2) evolution rate of 2,900μmol·g−1·h−1.This work provides an isolation strategy for constructing promising single-atom metal catalyst for photocatalysis and beyond.

关键词： Ni or Co single atoms cocatalyst anatase TiO_(2)(TiO_(2)(A)) photocatalytic H_(2)evolution

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