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Direct seawater splitting for hydrogen production:Recent advances in materials synthesis and technological innovation

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Green Energy & Environment 2025年第1期10卷 11-33页

作者： Yilin Zhao Zhipeng Yu Aimin Ge Lujia Liu Joaquim Luis Faria Guiyin Xu Meifang Zhu State Key Laboratory for Modification of Chemical Fibers and Polymer materials Center for Advanced Low-dimension MaterialsCollege of Materials Science and EngineeringDonghua UniversityShanghai201620China International Iberian nanotechnology Laboratory(INL) Avenida Mestre Jose VeigaBraga4715-330Portugal The MacDiarmid Institute for advanced materials and nanotechnology School of Chemical and Physical SciencesVictoria University of WellingtonWellington6012New Zealand LSRE-LCM-Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and materials Faculty of EngineeringUniversity of PortoRua Dr.Roberto Frias s/nPorto4200-465Portugal ALiCE-Associate Laboratory in Chemical Engineering Faculty of EngineeringUniversity of PortoRua Dr.Roberto Frias s/nPorto4200-465Portugal

Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil ***,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in ***,producing hydrogen on an industrial scale is challenging due to the high production *** present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater *** the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater *** the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater ***,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.

关键词： Seawater splitting Catalyst Membranes Mixed seawater systems Self-powered systems

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Bimetallic Single‑Atom Catalysts for Water Splitting

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Nano-Micro Letters 2025年第1期17卷 1-45页

作者： Megha A.Deshmukh Aristides Bakandritsos Radek Zbořil nanotechnology Centre Centre for Energy and Environmental TechnologiesVŠB–Technical University of Ostrava17.listopadu 2172/1570800 Ostrava‑PorubaCzech Republic Regional Centre of advanced Technologies and materials Czech Advanced Technology and Research Institute(CATRIN)Palacky University OlomoucŠlechtitelů241/2778371 Olomouc–HoliceCzech Republic

Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent *** field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their ***,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed *** offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation *** review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water *** subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination ***,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.

关键词： Single-atom catalysts Single-atom dimers Hydrogen evolution Oxygen evolution Water splitting

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Tuning the interfacial reaction environment via pH-dependent and induced ions to understand C–N bonds coupling performance in NO3- integrated CO2 reduction to carbon and nitrogen compounds over dual Cu-based N-doped carbon catalyst

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Journal of Energy Chemistry 2025年第1期100卷 273-285页

作者： Tianhang Zhou Chen Shen Zhenghao Wu Xingying Lan Yi Xiao College of Carbon Neutrality Future Technology State Key Laboratory of Heavy Oil Processing China University of Petroleum (Beijing) Institute of materials Science TU Darmstadt Department of Chemistry Xi'an Jiaotong-Liverpool University Department of Mechanical and Mechatronics Engineering and Waterloo Institute of Nanotechnology University of Waterloo Waterloo

Dual atomic catalysts （DAC）,particularly copper （Cu2）-based nitrogen （N） doped graphene,show great potential to effectively convert CO2and nitrate （NO3-） into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N ***,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO2reduction reaction （CO2RR）.To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu2-based N-doped carbon (Cu2N6C10) catalyst for *** calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction *** to the sluggishness of CO2,the formation of a solvation electric layer by anions （F-,Cl-,Br-,and I-） and cations (Na+,Mg2+,K+,and Ca2+) leads to electron transfer towards the Cu *** process significantly accelerates the reduction of *** results reveal that*CO intermediates play a pivotal role in N-integrated ***,the Cu2-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to *** findings reveal that through the process of a condensation reaction between*CO and NH2OH for urea synthesis,*NO3-is reduced to*NH3,and*CO2to*CCO at dual Cu atom *** dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH3and the ketene ***,we found that the I-and Mg2+ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca2+were ***,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shift

关键词： Condensation reactions

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Effect of alkaline metal ions on the photoluminescence properties of Eu^(3+)-doped Ca_3Al_2O_6 phosphors

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Journal of Rare Earths 2016年第12期34卷 1193-1198页

作者： Kyeongsoon Park Joon Woo Pi Deshmukh Abdul Hakeem Faculty of nanotechnology and advanced materials Engineering Sejong University

Ca3–xAl2O6：x Eu^3＋（0.02≤x≤0.10） and Ca（2.92）Al2O6：0.04Eu^3＋,0.04M^＋（M^＋=Li^＋, Na^＋, and K^＋） phosphors were prepared by sol-gel method and their photoluminescence properties were investigated. The crystal structure of the annealed Ca3–xAl2O6：x Eu^3＋ and Ca（2.92）Al2O6：0.04Eu^3＋,0.04M^＋ phosphors was analyzed with X-ray diffraction（XRD）. The size and morphological characteristics of the annealed phosphors were investigated with a field emission scanning electron microscope（FE-SEM）. The photoluminescence properties were evaluated with a spectrofluorometer. The phosphors were effectively excited by the light of 396 nm and showed intense red emission at 616 nm, which originated from the 5D0→7F2 transition of Eu^3＋. Among the prepared phosphors, the Ca（2.96）Al2O6：0.04Eu^3＋ phosphor showed the strongest emission intensity and the highest color purity. The addition of alkaline metal ions（Li^＋, Na^＋, and K^＋） to Ca（2.96）Al2O6：0.04Eu^3＋ phosphor degraded the emission intensity and color purity.

关键词： phosphor photoluminescence emission sol-gel method Eu3+ rare earths

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Preparation and infrared emissivities of alkali metal doped ZnO powders

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Journal of Central South University 2014年第9期21卷 3449-3455页

作者：李会会黄云霞李智敏姚银华张淑敏 School of advanced materials and nanotechnology Xidian University

Alkali metal(Li, Na, K) doped ZnO powders were synthesized by solid-state reaction at different calcination temperatures and holding time. Effects of holding time and K sources on the infrared emissivity of ZnO were investigated. The structure and surface morphologies of samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The UV-Vis absorption and infrared emissivities were investigated by a UV-Vis spectrophotometer and an infrared emissometer, respectively. XRD patterns confirm the wurtzite structure of the as prepared samples with single phase. Smooth grain surfaces are detected in all doped ZnO samples, while ZnO:Li and ZnO:Na present the aggregation of grains. The redshifts in the optical band-gap are observed in K-, Na-, and Li-doped ZnO with the values 3.150, 3.144, and 3.142 eV. Due to better crystalline quality, ZnO:K shows a lower emissivity than others. The emissivity of K-doped ZnO decreases to the minimum value(0.804), at 1200 °C and holding 2 h. Compared with KNO3 as K source, K2CO3 doped ZnO has lower emissivities.

关键词： infrared emissivity alkali metal crystalline quality optical band-gap ZnO powders

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Mechanical properties of the A356 aluminum alloy modified with La/Ce

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Journal of Rare Earths 2013年第8期31卷 811-816页

作者： E. Aguirre-De la Torre R. Pérez-Bustamante J. Camarillo-Cisneros C.D. Gómez-Esparza H.M. Medrano-Prieto R. Martínez-Sánchez advanced materials Research Center (CIMAV) National Laboratory of Nanotechnology

The research of rare earths for the synthesis of materials with improved mechanical performance is of great interest when they are considered for potential applications in the automotive industry. In this regard, the effect on the mechanical properties and microstmcture of the automotive A356 aluminum alloy reinforced with 0.2 （wt.%） AI-6Ce-3La （ACL） was investigated. The ACL was added to the melted A356 alloy in the as-received condition and processed by mechanical milling. In the second route, the effect of the ACL processed by mechanical milling and powder metallurgy techniques was investigated, and compared with the results ob- tained from the A356 alloy strengthened with ACL in the as-received condition. Microstmctural properties were evaluated by means of X-ray diffraction in order to observe the solubility of Ce/La in the A1 matrix. In addition, electron microscopy was employed in or- der to investigate the effect of milling time on the size and morphology of La/Ce phase under milling process. Mechanical properties of the A356 alloy modified with ACL were measured by hardness and tensile test. For comparison unmodified specimens of the A356 were characterized according to the previous procedure. The microstructural and mechanical characterization was carried out in specimens alter solution and artificial aging. Observations in scanning electron microscopy indicated a homogeneous dispersion of La/Ce phases by using both routes; however, mechanical results, in the modified A356 alloy with the ACL in the as-received condi- tion, showed an improvement in the mechanical performance of the A356 alloy over that reinforced with the ACL mechanically milled.

关键词： A356 rare earths mechanical milling mechanical properties

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Defects‑Rich Heterostructures Trigger Strong Polarization Coupling in Sulfides/Carbon Composites with Robust Electromagnetic Wave Absorption

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Nano-Micro Letters 2025年第1期17卷 528-547页

作者： Jiaolong Liu Siyu Zhang Dan Qu Xuejiao Zhou Moxuan Yin Chenxuan Wang Xuelin Zhang Sichen Li Peijun Zhang Yuqi Zhou Kai Tao Mengyang Li Bing Wei Hongjing Wu Mengyang Li Bing Wei Hongjing Wu School of Physics Xidian UniversityXi’an 710071People’s Republic of China School of advanced materials and nanotechnology State Key Discipline Laboratory of Wide Band Gap Semiconductor TechnologyXidian UniversityXi’an 710071People’s Republic of China School of Microelectronics Xidian UniversityXi’an 710071People’s Republic of China School of Telecommunication Engineering Xidian UniversityXi’an 710071People’s Republic of China MOE Key Laboratory of Material Physics and Chemistry Under Extraordinary School of Physical Science and TechnologyNorthwestern Polytechnical UniversityXi’an 710072People’s Republic of China The Ministry of Education Key Laboratory of Micro and Nano Systems forAerospace School of Mechanical EngineeringNorthwestern PolytechnicalUniversityXi’an 710072People’s Republic of China

Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic *** methods,however,constrain their delicate ***,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon *** unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial ***“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first ***,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric *** defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.

关键词： Defects-rich heterointerfaces Sulfides Polarization coupling Electromagnetic wave absorption

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Synthesis of Au-Cu Nano-Alloy from Monometallic Colloids by Simultaneous Pulsed Laser Targeting and Stirring

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Nano-Micro Letters 2011年第4期3卷 256-263页

作者： Mansoureh Ganjali Monireh Ganjali Soraia Khoby Mohammad Ali Meshkot nanotechnology and advanced materials Department Material and Energy Research Center

Experimental work has been focused on the formation of alloyed Au-Cu nanoparticles under simultaneous laser exposure and mechanical stirring of mixed monometallic colloids, here referred to as dual procedure. As a feed for the dual procedure, Au and Cu monometallic nanoparticle colloids have been using a laser ablation technique. To accomplish this, bulk targets were ablated with 1064 nm wavelength Nd: YAG laser in a pure acetone(99.99%) environment. Ultraviolet-visible optical absorption spectrometry, transmission electron microscopy, X-ray diffraction and X-ray fluorescence technique have been used to characterize the nanoparticles. It has been found that experimental conditions such as stirring and laser parameters strongly affect the synthesized particle properties, including the size, shape, composition and stability of the nanoparticles. Alloy nanoparticles containing 39% Au – 61% Cu have also been prepared in the same process, but in two forms of a homogeneous alloy and a core-shell structure.

关键词： Laser ablation Alloyed Au-Cu nanoparticles Dual procedure Laser exposure Mechanical mixing Core-shell

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Synthesis of Octapod Cu-Au Bimetallic Nanocrystal with Concave Structure through Galvanic Replacement Reaction

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Journal of Electronic Science and Technology 2020年第2期18卷 151-158页

作者： Zhen-Ni Wang Qiang Li Zhen-Huan Zhao Xiao-Mei Tong School of advanced materials and nanotechnology Xidian UniversityXi’an 710126

We synthesized octapod Cu-Au bimetallic alloy with a concave structure by employing a replacement reaction between Au PPh3Cl and Cu nanocubes. Using the Cu nanocube as sacrificial templates, we have successfully generated high-active sites on alloy nanocrystals by carefully tuning the replacement reaction and growth. The key is to afford the proper concentration of Au PPh3Cl-TOP to the reaction solution. When the Au precursor with high concentration is injected into the galvanic replacement reaction, the growth dominated the process and hollowed octapod Cu-Au alloy was obtained. In contrast, when the concentration of the Au precursor is low, the replacement reaction can only take place at the nanocrystals, leading to generate Cu-Au nanocages. This work provides an effective strategy for the preparation of hollow bimetallic nanocrystals with high-active sites.

关键词： solution. crystal concave

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Thermodynamic Aspects of Nanostructured CoAl Intermetallic Compound during Mechanical Alloying

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Journal of materials Science & Technology 2011年第7期27卷 601-606页

作者： S.N. Hosseini T. Mousavi F. Karimzadeh M.H. Enayati Department of materials Engineering Nanotechnology and Advanced Materials Institute Isfahan University of Technology84156-83111 Iran

The nanostructured CoAl intermetallic compound was produced by mechanical alloying （MA） of the Co50Al50 elemental powder mixture in a planetary high energy ball mill. The ordered B2-CoAl structure with the grain size of about 6 nm was formed via a gradual reaction after 10 h of MA. A thermodynamic analysis of the process was also done. The results showed that the intermetallic compound of CoAl had the minimum Gibbs free energy compared to solid solution and amorphous states indicating the initial MA product was the most stable phase in the Co-Al system which was changed to a partially disordered structure with a steady long-range order of 0.82 at further milling. This amount of disordering caused the enthalpy of final product to show an increase of about 5.1 kJ·mol-1. Calculation of enthalpy related to the triple defect formation revealed that the enthalpy required for Al anti-sites formation was about 3 times greater than that for Co anti-sites formation.

关键词： Intermetallics CoAl Nanostructured materials Mechanical alloying Thermodynamics

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