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稀有金属（英文版）
稀有金属（英文版）

屠海令

双月刊

1001-0521

rmchina@263.net

010-82240869

100083

学院路30号

稀有金属（英文版）/Journal Rare MetalsCSCDCSTPCD北大核心EISCI
查看更多>>本刊以稀有金属材料研究、开发和冶炼为特色，主要报道稀有金属和部分有色金属在材料研制、合金加工、选矿、冶炼、理化分析测试等方面的最新研究成果，同时报道超导材料、半导体材料、复合材料、陶瓷材料、贮氢材料、磁性材料和纳米材料的研制与性能。
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    PVP/PAN-derived porous carbon fiber for zinc-ion hybrid supercapacitors

    Shu-Hua YangWen-Qing FuYan-Wei CuiBing-Qiang Cao...
    3066-3073页
    查看更多>>摘要：Porous carbon fibers are promising cathodes for zinc-ion hybrid supercapacitors(ZHSs)owing to their abundant active sites,great conductivity,and stable physi-cal and chemical properties.However,designing a proper preparation technique to regulate the microstructure of carbon fibers still remains a great challenge.Here,a polyvinylpyrrolidone/po-lyacrylonitrile(PVP/PAN)-derived porous carbon fiber is developed via the PVP/PAN blend electrospinning and hydrothermal selective PVP removal strategy.The hydrothermal selective PVP removal strategy can effectively avoid a cross-linking between PVP and PAN during the traditional stabilization at air atmo-sphere.In PVP/PAN-derived porous carbon fiber,the suf-ficient micropores provide abundant space for the Zn2+storage,whereas the proper mesopores contribute to the fast ion transfer.These hierarchical porous structures endow ZHSs with high specific capacity and high-rate performance.The ZHS assembled with the optimal PVP/PAN-derived porous carbon fiber(PVP-PANC-0.8)dis-plays an outstanding specific capacity of 208 mAh·g-1,high rate capability(49.5％)from 0.5 to 5 A·g-1,and 72.25％capacity retention after 10,000 cycles at 0.5 A·g-1.
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    Spontaneous anchoring Cl into α-Co(OH)2 as efficient and stable oxygen reduction electrocatalysts for seawater battery

    Wang ZhengXue-Rong ZhengQi LuYan-Hui Cao...
    3074-3083页
    查看更多>>摘要：Seawater battery is an advanced energy storage system that enables conversion of chemical energy to electricity by consuming metals,dissolved oxygen and seawater in anode,cathode and electrolyte,respectively.However,the oxygen reduction reaction(ORR)activity and stability of electrocatalysts can be easily deactivated due to the severe Cl-permeation and corrosion in seawater electrolyte.Herein,we developed a structural buffer engi-neering strategy by spontaneously anchoring Cl-into α-Co(OH)2 as efficient and stable ORR electrocatalysts,in which the ultrathin α-Co(OH)2 nanosheets were synthe-sized using an ultrafast solution high-temperature shock(SHTS)strategy.The large lattice space(～0.8 nm)of layered α-Co(OH)2 ensured the spontaneously penetration of Cl-into the lattice structure and replaced part of OH-to form α-Co(OH)2-xClx.The continuous leaching and compensating of saturated Cl in α-Co(OH)2-xClx could enhance the Cl-corrosion resistance and modulate elec-tronic structure of Co metallic sites,thus improving the ORR electrocatalytic activity and stability in seawater electrolyte.The α-Co(OH)2-xClx seawater batteries display superior onset and half-wave potentials of 0.71 and 0.66 V,respectively,which are much better than the counterparts of α-Co(OH)2 and of β-Co(OH)2 with no Cl-penetrating and no buffer structure.The α-Co(OH)2-xClx-based sea-water batteries display stable open-circuit potential of 1.69 V and outstanding specific capacity of 1345 mAh·g-1.
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    Bimetallic NiCoP catalysts anchored on phosphorus-doped lignin-based carbon for robust oxygen evolution performance

    Ling-Ying-Zi XiongBo-Wen LiuLei DuYue-Kuan Zhou...
    3084-3095页
    查看更多>>摘要：Oxygen evolution reaction(OER)catalysts are the key core materials that determine the performance of fuel cells,metal-air batteries,electrolytic water decomposition,and other applications.In this work,a green lignin-based non-precious metal OER catalyst was prepared by a simple strategy.Firstly,carboxylated lignin was used to complex Ni and Co in situ,and then they were placed with sodium hypophosphite in the same tube furnace for upstream and downstream high-temperature calcination to construct a lignin carbon-based Ni-Co bimetallic OER catalyst(NiCoP@C).The synthesized catalyst is a porous bimetallic phosphide with a three-dimensional network structure and high-density electrochemical active sites.NiCoP@C exhibited favorable catalytic activity for the oxygen evolu-tion reaction(OER)with overpotential of 280 mV at 10 mA·cm-2 and a Tafel slope of 77 mV·dec-1.Addition-ally,it exhibited remarkable durability during usage.Density functional theory(DFT)calculations revealed that by leveraging the distinctive structure of transition metal phosphide nanoparticles incorporated into a reticulated substrate,the NiCoP@C catalyst offered an increased number of active sites for OER catalysis,significantly enhancing its stability during practical applications.The present study broadens the utilization pathways of biomass to"turn waste into treasure,"aligning the development concept of green sustainable development.
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    Metal complexes of bipyridine-functionalized covalent organic frameworks as efficient electrocatalysts for oxygen evolution reaction

    Zhuang-Zhuang WuTian XiaYing LiangYong-Peng Li...
    3096-3106页
    查看更多>>摘要：Electrocatalytic water splitting is considered a clean and practical method for producing energy.In this study,COF-Bpy,a bipyridine-functionalized covalent organic framework(COF),was prepared via post-synthetic modifi-cation,after which electrocatalysts for the oxygen evolution reactions(OER)were formed through coordination to single-or double-transition metals(Fe,Co,Ni,FeCo,FeNi or CoNi).COF-Bpy@FeNi delivered the best OER performance among the studied electrocatalysts,with an overpotential of 399 mV at 10 mA·cm-2 in an alkaline electrolyte(1.0 mol·L-1 KOH aqueous).Notably,the electrocatalytic performance of COF-Bpy@FeNi showed slight degradation during durability test-ing,which is ascribable to its irreversible benzoquinoline structure and strong metal coordination.As expected,COF-Bpy@FeNi exhibited a low overpotential of 347 mV at a turnover frequency(TOF)of 0.1 s-1,which suggests that COF-Bpy@FeNi possesses excellent intrinsic electrocatalytic OER activity.Finally,density functional theory(DFT)cal-culations reveal that the Ni site plays a major role,while the Fe site adjusts the electronic structure of the Ni ions,which rationalizes the excellent OER properties of COF-Bpy@FeNi.This study not only provides a simple and efficient method for complexing COFs with transition metals,but also offers a novel strategy for designing porous organic polymer electrocatalysts.
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    Transition metal clusters with precise numbers of atoms anchored on graphdiyne as multifunctional electrocatalysts for OER/ORR/HER:a computational study

    Xin-Yang LiuJing-Wei LiuGang LiJing-Xiang Zhao...
    3107-3117页
    查看更多>>摘要：Subnanometer metal clusters play an increas-ingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT)calculations,the catalytic activities of transition metal clusters with precise numbers of atoms supported on graphdiyne(TM1-4@GDY,TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Pd,Ir,Pt)were investigated for oxygen evolution reactions(OER),oxygen reduction reactions(ORR)and hydrogen evolution reactions(HER).The computed results reveal that the Pd2,Pd4 and Pt1 anchored graphdiyne can serve as trifunctional catalysts for OER/ORR/HER with the over-potentials of 0.49/0.37/0.06,0.45/0.33/0.12 and 0.37/0.43/0.01 V,respectively,while Pd1 and Pt2@graphdiyne can exhibit excellent catalytic performance for water splitting(OER/HER)with the overpotentials of 0.55/0.17 and 0.43/0.03 V.In addition,Ni1 and Pd3 anchored GDY can per-form as bifunctional catalysts for metal-air cells(OER/ORR)and fuels cells(ORR/HER)with the overpotentials of 0.34/0.32 and 0.42/0.04 V,respectively.Thus,by pre-cisely controlling the numbers of atoms in clusters,the TM1-4 anchored graphdiyne can serve as promising mul-tifunctional electrocatalysts for OER/ORR/HER,which may provide an instructive strategy to design catalysts for the energy conversation and storage devices.
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    Insights into photocatalytic mechanism over a novel Cu2WS4/MoS2 S-scheme heterojunction

    Wei ZhaoJi-Hui CaoJun-Jie LiaoYun Liu...
    3118-3133页
    查看更多>>摘要：A novel efficient Cu2WS4/MoS2 step-scheme(S-scheme)heterojunction photocatalyst was constructed for the first time and applied in the removal of environ-mental pollutants.Among the as-prepared photocatalysts,the Cu2WS4/MoS2-8％heterojunction photocatalyst demonstrates the optimal photocatalytic performance,with the catalytic oxidation efficiency of tetracycline(TC)and the catalytic reduction efficiency of Cr6+reaching 93.3％and 82.1％,respectively.The excellent catalytic properties of Cu2WS4/MoS2 heterojunction photocatalysts are attrib-uted to the effective separation pathways of charges and the presence of S-scheme heterojunctions,together with stronger redox capabilities.It is speculated that the pho-togenerated carrier migration path of the Cu2WS4/MoS2 catalyst follows the typical S-scheme photocatalytic mechanism,which is verified by the in-depth experimental study and simulated calculations including the electron paramagnetic resonance(EPR)analysis,free radical quenching experiments,charge density distribution,and simulated built-in electric field formation at the interface,which acts as driving force to promote the separation of photoinduced electrons and holes.Finally,the photocat-alytic mechanism of S-scheme photogenerated carrier migration for the Cu2WS4/MoS2 catalyst is revealed based on the systematic experimental techniques and simulated calculations,accounting for its superior photocatalytic oxidation and reduction activities.This study provides inspiring implications to develop high-efficient S-scheme photocatalytic systems for versatile applications in solar-energy conversion.
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    Visible-light-driven photocatalysis degradation of antibiotic pollutants by La-doped CeO2 nanorods:synergy of La doping and oxygen vacancy

    Shi-Hai CaoJing-Ru QuYu-Qi ZhaoYun-Tong Sun...
    3134-3145页
    查看更多>>摘要：Elemental doping is an effective strategy to enhance photocatalytic activity and extend the light absorption range of single-component photocatalysts.In this work,a series of La-doped CeO2 nanorods(La-CeO2-x)with La content of 1 wt％-15 wt％are synthesized by a simple hydrothermal method and further used as photo-catalyst for sulfamerazine(SMR)degradation.The pre-pared La-CeO2-x nanorods exhibit a great improvement in electron-hole pair migration and visible-light response due to the synergistic effect of abundant oxygen vacancies and heterogeneous elements(La).Consequently,La-CeO2-x exhibited excellent visible-light photocatalytic performances and chemical stability for SMR degradation,the La-CeO2-5 sample achieved the highest SMR degra-dation rate of 81％,which was 3.4 times higher than that of the original CeO2.Furthermore,three possible degradation pathways of SMR in La-CeO2 photocatalytic reactions were proposed by liquid chromatography-mass spectrom-etry technique.Finally,density functional theory calcula-tions were carried out to provide an in-depth understanding of the structure-performance relationships.Considering its excellent properties and better photocatalytic performance,this study demonstrates that La doping in CeO2 is an effective way to increase oxygen vacancy and improve the photochemical properties of photocatalysts.
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    Coupling N-doping and confined Co3O4 on carbon nanotubes by polydopamine coating strategy for pleiotropic water purification

    Wen-Long TuGang WangYue ZhangHong-Yang Zhu...
    3146-3160页
    查看更多>>摘要：The development of effective and sustainable solutions for pleiotropic water purification becomes urgent and attractive.Heterogeneous Fenton-like catalysts for activation of peroxymonosulfate(PMS)to purify organic wastewater show great promise.In this work,by tuning metal loading with an in-situ polydopamine coating strat-egy,oxygen vacancy-enriched Co3O4 loading on N-doped carbon nanotubes(CNTs)were constructed to enhance PMS activation efficiency for pollutants degradation.Impressively,the obtained modified CNTs afford a well-developed N-containing network structure,which is further endowed with abundant Co(Ⅱ)/Co(Ⅲ)redox cycles and significant metal-carbon interactions.In particular,the surface N doping in CNTs might induce the oriented enrichment of pollutants around the catalyst,which reduces the migration distance and correspondingly improves the utilization of reactive oxidative species.The electron transfer efficiency of the catalyst can be further improved by incorporating oxygen vacancy-enriched Co3O4.The performance results show that the optimal NC/Co-1 could mineralize 20 × 10-6 of bisphenol A(BPA)by almost 98％in 8 min.A low reaction activation energy(26.05 kJ·mol-1)in BPA degradation was demonstrated by the NC/Co-1.More importantly,NC/Co-1 can inherit excellent degradation performance towards oxytetracy-cline,2,4-dichlorophenol,and tetracycline,showing wide practical flexibility.In addition,by virtue of the pho-tothermal conversion property,NC/Co-1 achieves an additive function for interfacial solar water evaporation(1.84 kg·m-2·h-1,112.51％),showing impressive potential for clean water recovery under complicated environmental pollution conditions.
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    Z-scheme Bi4O5Br2/NH2-MIL-125(Ti)heterojunctions enable exceptional visible photocatalytic degradation of organic pollutant

    Feng HuangMuhammad HumayunGang LiTing-Ting Fan...
    3161-3172页
    查看更多>>摘要：One key strategy to enhance photocatalytic performance is to improve the transfer and separation efficiency of photogenerated carriers by building optimized heterojunctions.Herein,novel Bi4O5Br2/NH2-MIL-125(Ti)Z-scheme heterojunctions are fabricated and used as photocatalysts for organic pollutant photodegradation.The NH2-MIL-125(Ti)nanosheets are exfoliated via a self-de-veloped alkali solution stripping approach and then uni-formly decorated on Bi4O5Br2.The as-prepared Bi4O5Br2/NH2-MIL-125(Ti)presents more than 90％degradation of various pollutants,outperforming the counterpart individ-ual ones.The various characterization results suggest that the enhanced degradation rate is due to the more intimate face-to-face interfacial contact of the lamellar Z-scheme heterojunction materials,in which the migration path of carriers from the material's interior to the surface can be reduced,in turn enhancing migration efficiency and separation capability significantly.A possible photocat-alytic reaction mechanism is proposed based on the pho-toelectric behaviors,radical trapping experiments and liquid chromatography mass spectrometry analysis.This work promotes the development of new photocatalytic materials for heterojunctions with face-to-face interfacial contacts,as well as the effective purification of wastewater in environmental remediation.
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    Efficient piezo-catalytic dye degradation using piezoelectric 6H-SiC under harsh conditions

    Lin-Lin ZhouTao YangKang WangLai-Pan Zhu...
    3173-3184页
    查看更多>>摘要：The development of novel piezoelectric cata-lysts against harsh conditions is indeed crucial for improving the piezo-catalytic degradation efficiency of colored organic dyes in wastewater.In this work,6H-SiC nanoparticles(NPs)are utilized to piezo-catalytic degrade rhodamine B(RhB)and methylene blue(MB)under ultrasonic vibration for the first time.The degradation efficiency of RhB and MB reaches 98.8％and 98.7％within 80 min.The piezoelectricity of 6H-SiC is compre-hensively analyzed by the piezoresponse force microscope(PFM)and finite element method(FEM).The strong oxi-dizing active free radicals generated by the continuous piezoelectric polarized electric field of 6H-SiC,i.e.,·O2-and·OH,induce the decomposition reactions of colored organic dyes in solution.And the dyes are proven to degrade to harmless or less-harmful products gradually during the piezo-catalysis process by high-performance liquid chromatography tandem mass spectrometry(HPLC-MS).Moreover,RhB is also decomposed efficiently by 6H-SiC NPs under acidic and alkaline conditions.These results prove the feasibility of 6H-SiC for decomposing common water pollutants under harsh conditions and provide a new perspective for water purification.
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