Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscalin...Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.展开更多
Sea cucumber Holothuria leucospilota is one of the most widespread tropical holothurian species.In this study,eukaryotic organism composition in foregut and hindgut contents of H.leucospilota and surrounding sediments...Sea cucumber Holothuria leucospilota is one of the most widespread tropical holothurian species.In this study,eukaryotic organism composition in foregut and hindgut contents of H.leucospilota and surrounding sediments was assessed by 18S rRNA gene high-throughput sequencing.Eukaryon richness and diversity in the habitat sediments were significantly higher than those in foregut and hindgut contents of the sea cucumbers(P<0.05).The foregut content group,hindgut content group,and marine sediment group sequences were respectively assigned to 18.20±1.32,19.40±1.03,and 21.80±0.37 phyla.In the foregut contents,Nematoda(20.18%±9.59%),Mollusca(16.12%±10.49%),Chlorophyta(10.04%±4.85%),Annelida(8.72%±10.93%),Streptophyta(8.46%±4.65%),and Diatomea(5.99%±2.01%)were the predominant phyla,which showed the eukaryotic food sources of H.leucospilota were primarily belong to the above phyla.The predominant phyla in the hindgut contents were Streptophyta(45.55%±17.32%),Mollusca(4.93%±4.82%),Arthropoda(5.37%±3.08%),Diatomea(3.88%±2.34%),and Chlorophyta(3.79%±1.59%);and Annelida(37.80%±17.00%),Arthropoda(24.49%±12.53%),Platyhelminthes(7.14%±3.02%),Nematoda(4.14%±0.91%),and Diatomea(5.11%±1.35%)had large contents in the sediments.The comparatively high content of Paris genus in phylum Streptophyta in foregut contents indicated that land plants were one of the primary food sources of H.leucospilota,however the significantly higher contents of Streptophyta in hindgut contents than that in foregut contents might suggest a large part of the terrigenous detritus ingested might not be digested by H.leucospilota.UPGMA and PCoA analysis revealed that eukaryotic organism composition differed significantly between foregut contents of H.leucospilota and ambient sediments,indicating selective feeding feature of H.leucospilota.This study provided useful references for artificial feed of tropical sea cucumbers and enhanced understanding of the ecological roles of detritus-feeding macrobenthos.展开更多
Cutaneous squamous cell carcinoma(cSCC),a type of non-melanoma skin cancer(NMSC),is the most common malignancy worldwide.Thioredoxin(TXN)domain-containing protein 9(TXNDC9)is a member of the TXN family that is importa...Cutaneous squamous cell carcinoma(cSCC),a type of non-melanoma skin cancer(NMSC),is the most common malignancy worldwide.Thioredoxin(TXN)domain-containing protein 9(TXNDC9)is a member of the TXN family that is important in cell differentiation.However,the biological function of this protein in cancer,particularly cSCC,is still unknown.In the present study,our experiments revealed the protective effects of TXNDC9 on UV-B-irritated cSCC cells.The initial findings showed that TXNDC9 is significantly upregulated in cSCC tissue and cells compared to normal skin tissue and keratinocytes.UV-B radiation robustly induces the expression of TXNDC9,and UV-B-induced cSCC cell death is boosted by TXNDC9 deficiency.Moreover,cSCC cells lacking TXNDC9 displayed attenuated activation of the NF-κB pathway.Additional studies by inhibiting TXNDC9 confirmed this finding,as TXNDC9 deficiency attenuated UV-B radiation-induced translocation of NF-κB p65 from the cytoplasm to the nucleus of cSCC.In conclusion,our work demonstrates the biological roles of TXNDC9 in cSCC progression and may provide a novel therapeutic target to treat cSCC in the future.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically re...Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically reduce CO_(2) emission and contribute to carbon-neutral cycle. E cient electrocatalytic reduction of chemically inert CO_(2) is challenging from thermodynamic and kinetic points of view. Therefore,low-cost,highly e cient,and readily available electrocatalysts have been the focus for promoting the conversion of CO_(2). Very recently,interface engineering has been considered as a highly e ective strategy to modulate the electrocatalytic performance through electronic and/or structural modulation,regulations of electron/proton/mass/intermediates,and the control of local reactant concentration,thereby achieving desirable reaction pathway,inhibiting competing hydrogen generation,breaking binding-energy scaling relations of intermediates,and promoting CO_(2) mass transfer. In this review,we aim to provide a comprehensive overview of current developments in interface engineering for CO_(2) RR from both a theoretical and experimental stand-point,involving interfaces between metal and metal,metal and metal oxide,metal and nonmetal,metal oxide and metal oxide,organic molecules and inorganic materials,electrode and electrolyte,molecular catalysts and electrode,etc. Finally,the opportunities and challenges of interface engineering for CO_(2) RR are proposed.展开更多
Vapor deposition and three-dimensional(3D)printing technology are considered to be conventional methods to achieve patterned metal film preparation through the assistance of masks and high temperature.Therefore,there ...Vapor deposition and three-dimensional(3D)printing technology are considered to be conventional methods to achieve patterned metal film preparation through the assistance of masks and high temperature.Therefore,there are still some challenges in fabricating metal films in template-free and normal temperature environment.In this work,we report a flexible and rapid laser metal transfer(LMT)technique for fabricating the various metal films(Cu,Ni,Sn,Al,Fe,and Ag)with different patterns without templates on arbitrary substrates(glass,polyimide(PI)films,and aluminum nitride(AlN)ceramic).Especially,the obtained transparent conductive glass displays high transmittance(more than 90%)and adjustable resistances(≈5Ω).According to the Joule effect,the interface resistance between Cu particles and copper oxide coating produces the high temperature approximately 280℃ at 2 V in a short time(≈60 s)and remains stable at 120℃ over 12 h.At last,the multifunctional glass with Cu patterns also shows excellent bactericidal activity(≈95%).This work demonstrates that laser metal transfer is an exceeding effective means of fabricating the micro/nano structures with potential applications in functional devices.展开更多
Transition metal nitride/carbide(TMN/C)have been actively explored as low-cost hydrogen evolution reaction(HER)electrocatalysts owing to their Pt-like physical and chemical properties.Unfortunately,pure TMN/C suffers ...Transition metal nitride/carbide(TMN/C)have been actively explored as low-cost hydrogen evolution reaction(HER)electrocatalysts owing to their Pt-like physical and chemical properties.Unfortunately,pure TMN/C suffers from strong hydrogen adsorption and lacks active centers for water dissociation.Herein,we developed a switchable WO_(3)-based in situ gas–solid reaction for preparing sophisticated Fe-N doped WC and Fe-C doped WN nanoarrays.Interestingly,the switch of codoping and phase can be effectively manipulated by regulating the amount of ferrocene.Resultant Fe-C-WN and Fe-N-WC exhibit robust electrocatalytic performance for HER in alkaline and acid electrolytes,respectively.The collective collaboration of morphological,phase and electronic effects are suggested to be responsible for the superior HER activity.The smallest|ΔGH*|value of Fe-NWC indicates preferable hydrogen-evolving kinetics on the Fe-N-WC surface for HER under acid condition,while Fe-C-WN is suggested to be beneficial to the adsorption and dissociation of H_(2)O for HER in alkaline electrolyte.展开更多
The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a s...The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a sustainable and environmentally friendly energy source for human production and living.Very recently, photothermal catalysis has been proved to exhibit great advantages in reducing the reaction temperature, promoting the catalytic activity, and manipulating the reaction pathway in comparison with traditional thermal catalysis. In this review, we firstly introduced the fundamental mechanisms and categories of photothermal catalysis to understand the synergy or the difference between photochemical and thermochemical reaction pathways. Subsequently, the criteria and strategies for photothermal catalyst design are discussed in order to inspire the development of high-efficiency photothermal catalytic route by achieving intense absorption of broadband solar energy spectrum and high conversion capability of solar-to-heat. Recent progress in CO_(2)reduction achieved by photothermal catalysis was summarized in terms of production types. In the end, the future challenges and perspectives of photothermal catalytic CO_(2)reduction are presented. We hope that this review will not only deepen the understanding of photothermal catalysis, but also inspire the design, preparation and application of high-performance photothermal catalysts, aiming at alleviating non-renewable fossil energy consumption and carbon emissions for early carbon emission peak and carbon neutrality.展开更多
Stroke is an acute cerebro-vascular disease with high incidence and poor prognosis,most commonly ischemic in nature.In recent years,increasing attention has been paid to inflammatory reactions as symptoms of a stroke....Stroke is an acute cerebro-vascular disease with high incidence and poor prognosis,most commonly ischemic in nature.In recent years,increasing attention has been paid to inflammatory reactions as symptoms of a stroke.However,the role of inflammation in stroke and its underlying mechanisms require exploration.In this study,we evaluated the inflammatory reactions induced by acute ischemia and found that pyroptosis occurred after acute ischemia both in vivo and in vitro,as determined by interleukin-1β,apoptosis-associated speck-like protein,and caspase-1.The early inflammation resulted in irreversible ischemic injury,indicating that it deserves thorough investigation.Meanwhile,acute ischemia decreased the Sirtuin 1(Sirtl)protein levels,and increased the TRAF6(TNF receptor associated factor 6)protein and reactive oxygen species(ROS)levels.In further exploration,both Sirtl suppression and TRAF6 activation were found to contribute to this pyroptosis.Reduced Sirtl levels were responsible for the production of ROS and increased TRAF6 protein levels after ischemic exposure.Moreover,N-acetyl-L-cysteine,an ROS scavenger,suppressed the TRAF6 accumulation induced by oxygen-glucose deprivation via suppression of ROS bursts.These phenomena indicate that Sirtl is upstream of ROS,and ROS bursts result in increased TRAF6 levels.Further,the activation of Sirtl during the period of ischemia reduced ischemiainduced injury after 72 h of reperfusion in mice with middle cerebral artery occlusion.In sum,these results indicate that pyroptosis-dependent machinery contributes to the neural injury during acute ischemia via the Sirt1-ROS-TRAF6 signaling pathway.We propose that inflammatory reactions occur soon after oxidative stress and are detrimental to neuronal survival;this provides a promising therapeutic target against ischemic injuries such as a stroke.展开更多
The catalytic conversion of carbon dioxide(CO_(2))into high value-added chemicals is of great significance to address the pressing carbon cycle issues.Reticular chemistry of metal-organic frameworks(MOFs)-based materi...The catalytic conversion of carbon dioxide(CO_(2))into high value-added chemicals is of great significance to address the pressing carbon cycle issues.Reticular chemistry of metal-organic frameworks(MOFs)-based materials exhibits great potential and effectiveness to face CO_(2)challenge from capture to conversion.To date,the integrated nanocomposites of nanostructure and MOF have emerged as a powerful heterogeneous catalysts featured with multifold advantages including synergistic effects between the two interfaces,confinement effect of meso-and micropores,tandem reaction triggered by multiple active sites,high stability and dispersion,and so on.Given burgeoning carbon cycle and nanostructure@MOFs,this review highlights some of important advancements to provide a full understanding on the synthesis and design of nanostructure@MOFs composites to facilitate carbon cycle through CO_(2)photocatalytic,electrocatalytic,and thermal conversion.Afterward,the catalytic applications of some representative nanostructure@MOFs composites are categorized,in which the origin of activity or structure-activity relationship is summarized.Finally,the opportunities and challenges are proposed for inspiring the future development of nanostructure@MOFs composites for carbon cycle.展开更多
Electrocatalytic hydrogen production in alkaline media is extensively adopted in industry. Unfortunately, further performance improvement is severely impeded by the retarded kinetics, which requires the fine regulatio...Electrocatalytic hydrogen production in alkaline media is extensively adopted in industry. Unfortunately, further performance improvement is severely impeded by the retarded kinetics, which requires the fine regulation of water dissociation, hydrogen recombination, and hydroxyl desorption. Herein, we develop a multi-interface engineering strategy to make an elaborate balance for the alkaline hydrogen evolution reaction (HER) kinetics. The graphene cross-linked three-phase nickel sulfide (NiS-NiS_(2)-Ni_(3)S_(4)) polymorph foam (G-NNNF) was constructed through hydrothermal sulfidation of graphene wrapped nickel foam as a three-dimensional (3D) scaffold template. The G-NNNF exhibits superior catalytic activity toward HER in alkaline electrolyte, which only requires an overpotential of 68 mV to drive 10 mA·cm^(−2) and is better than most of the recently reported metal sulfides catalysts. Density functional theory (DFT) calculations verify the interfaces between nickel sulfides (NiS/NiS_(2)-Ni_(3)S_(4)) and cross-linked graphene can endow the electrocatalyst with preferable hydrogen adsorption as well as metallic nature. In addition, the electron transfer from Ni_(3)S_(4)/NiS_(2) to NiS results in the electron accumulation on NiS and the hole accumulation on Ni_(3)S_(4)/NiS_(2), respectively. The electron accumulation on NiS favors the optimization of the H* adsorption, whereas the hole accumulation on Ni_(3)S_(4) is beneficial for the adsorption of H_(2)O. The work about multi-interface collaboration pushes forward the frontier of excellent polymorph catalysts design.展开更多
Electroreduction of greenhouse gas CO_(2) into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change.However,the regulations of the selectivity to...Electroreduction of greenhouse gas CO_(2) into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change.However,the regulations of the selectivity towards C2 product and the competing hydrogen evolution reaction(HER)are major challenges for CO_(2) reduction reaction(CO_(2)RR).Here,we develop an interface-enhanced strategy by depositing a thin layer of nitrogen-doped graphene(N-G)on a Cu foam surface(Cu-N-G)to selectively promote the ethanol pathway in CO_(2)RR.Compared to the undetectable ethanol selectivity of pure Cu and Cu@graphene(Cu-G),Cu-N-G has boosted the ethanol selectivity to 33.1%in total Faradic efficiency(FE)at−0.8 V vs.reversible hydrogen electrode(RHE).The experimental and density functional theory(DFT)results verify that the interconnected graphene coating can not only serve as the fast charge transport channel but also provide confined nanospace for mass transfer.The N doping can not only trigger the intrinsic interaction between N in N-G and CO_(2) molecule for enriching the local concentration of reactants but also promote the average valence state of Cu for C–C coupling pathways.The confinement effect at the interface of Cu-N-G can not only provide high adsorbed hydrogen(Had)coverage but also stabilize the key*HCCHOH intermediate towards ethanol pathway.The provided interface-enhanced strategy herein is expected to inspire the design of Cubased CO_(2)RR electrocatalysts towards multi-carbon products.展开更多
Since the advent of graphene in 2004,two-dimensional(2D)materials had ignited the development of fascinating functional materials for almost 20 years.Currently,the main members of 2D materials family are graphene,tran...Since the advent of graphene in 2004,two-dimensional(2D)materials had ignited the development of fascinating functional materials for almost 20 years.Currently,the main members of 2D materials family are graphene,transition metal dichalcogenides(TMDs,MoS_(2),WS_(2),and others),MXenes(Ti_(3)C_(2),Ta_(4)C_(3),and others),Xenes(B,Si,P,Ge,and Sn),organic materials(COF,covalent organic frameworks),etc.The unique sheet-like morphology(single-or few-atomic-layer thickness)endow 2D materials with unconventional physicochemical properties for promising applications in catalysis,energy storage/conversion,electronics,biomedicine,sensors,etc.Nevertheless,the exploration and preparation of novel twodimensional materials with desired characteristics through highly controlled strategy remains one of the major challenges in this field.In a recent work from Nature Chemistry published on 10 February 2022,Liu et al.reported a new member,clusterphene,in the family of two-dimensional materials.展开更多
Spatial isolation of different functional sites at the nanoscale in multifunctional catalysts for steering reaction sequence and paths remains a major challenge.Herein,we reported the spatial separation of dual-site A...Spatial isolation of different functional sites at the nanoscale in multifunctional catalysts for steering reaction sequence and paths remains a major challenge.Herein,we reported the spatial separation of dual-site Au and RuO_(2)on the nanosurface of TiO_(2)(Au/TiO_(2)/RuO_(2))through the strong metal-support interaction(SMSI)and the lattice matching(LM)for robust photocatalytic hydrogen evolution.The SMSI between Au and TiO_(2)induced the encapsulation of Au nanoparticles by an impermeable TiO_(x)overlayer,which can function as a physical separation barrier to the permeation of the second precursor.The LM between RuO_(2)and rutile-TiO_(2)can increase the stability of RuO_(2)/TiO_(2)interface and thus prevent the aggregation of dual-site Au and RuO_(2)in the calcination process of removing TiO_(x)overlayer of Au.The photocatalytic hydrogen production is used as a model reaction to evaluate the performance of spatially separated dual-site Au/TiO_(2)/RuO_(2)catalysts.The rate of hydrogen production of the Au/TiO_(2)/RuO_(2)is as high as 84μmol h^(−1)g^(−1)under solar light irradiation without sacrificial agents,which is 2.5 times higher than the reference Au/TiO_(2)and non-separated Au/RuO_(2)/TiO_(2)samples.Systematic characterizations verify that the spatially separated dual-site Au and RuO_(2)on the nanosurface of TiO_(2)can effectively separate the photo-generated carriers and lower the height of the Schottky barrier,respectively,under UV and visible light irradiation.This study provides new inspiration for the precise construction of different sites in multifunctional catalysts.展开更多
基金financially supported by the National Key R&D Program of China (No. 2018YFB1502203-1)the Guangdong Basic and Applied Basic Research Foundation (No. 2021B1515120087)the Stable Supporting Fund of Shenzhen, China (No. GXWD20201230155427003-202007 28114835006)
文摘Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.
基金Supported by the National Natural Science Foundation of China(Nos.42166005,42076097)the Hainan Provincial Key Research and Development Program(No.ZDYF2021XDNY130)+1 种基金the Natural Science Foundation of Hainan Province(No.321RC1023)the State Key Laboratory of Marine Resource Utilization in South China Sea Open Project(No.MRUKF2021008)。
文摘Sea cucumber Holothuria leucospilota is one of the most widespread tropical holothurian species.In this study,eukaryotic organism composition in foregut and hindgut contents of H.leucospilota and surrounding sediments was assessed by 18S rRNA gene high-throughput sequencing.Eukaryon richness and diversity in the habitat sediments were significantly higher than those in foregut and hindgut contents of the sea cucumbers(P<0.05).The foregut content group,hindgut content group,and marine sediment group sequences were respectively assigned to 18.20±1.32,19.40±1.03,and 21.80±0.37 phyla.In the foregut contents,Nematoda(20.18%±9.59%),Mollusca(16.12%±10.49%),Chlorophyta(10.04%±4.85%),Annelida(8.72%±10.93%),Streptophyta(8.46%±4.65%),and Diatomea(5.99%±2.01%)were the predominant phyla,which showed the eukaryotic food sources of H.leucospilota were primarily belong to the above phyla.The predominant phyla in the hindgut contents were Streptophyta(45.55%±17.32%),Mollusca(4.93%±4.82%),Arthropoda(5.37%±3.08%),Diatomea(3.88%±2.34%),and Chlorophyta(3.79%±1.59%);and Annelida(37.80%±17.00%),Arthropoda(24.49%±12.53%),Platyhelminthes(7.14%±3.02%),Nematoda(4.14%±0.91%),and Diatomea(5.11%±1.35%)had large contents in the sediments.The comparatively high content of Paris genus in phylum Streptophyta in foregut contents indicated that land plants were one of the primary food sources of H.leucospilota,however the significantly higher contents of Streptophyta in hindgut contents than that in foregut contents might suggest a large part of the terrigenous detritus ingested might not be digested by H.leucospilota.UPGMA and PCoA analysis revealed that eukaryotic organism composition differed significantly between foregut contents of H.leucospilota and ambient sediments,indicating selective feeding feature of H.leucospilota.This study provided useful references for artificial feed of tropical sea cucumbers and enhanced understanding of the ecological roles of detritus-feeding macrobenthos.
基金supported by grants from the National Natural Science Fund Youth Fund of China(No.81901164)the Natural Science Foundation of Fujian Province(No.2020J02053)+2 种基金the Natural Science Foundation of Fujian Province(No.2020J01966)the Talent Introduction Project of the First Affiliated Hospital of Fujian Medical University(No.YJRC3813)the Startup Fund for Scientific Research,Fujian Medical University(2020QH2029).
文摘Cutaneous squamous cell carcinoma(cSCC),a type of non-melanoma skin cancer(NMSC),is the most common malignancy worldwide.Thioredoxin(TXN)domain-containing protein 9(TXNDC9)is a member of the TXN family that is important in cell differentiation.However,the biological function of this protein in cancer,particularly cSCC,is still unknown.In the present study,our experiments revealed the protective effects of TXNDC9 on UV-B-irritated cSCC cells.The initial findings showed that TXNDC9 is significantly upregulated in cSCC tissue and cells compared to normal skin tissue and keratinocytes.UV-B radiation robustly induces the expression of TXNDC9,and UV-B-induced cSCC cell death is boosted by TXNDC9 deficiency.Moreover,cSCC cells lacking TXNDC9 displayed attenuated activation of the NF-κB pathway.Additional studies by inhibiting TXNDC9 confirmed this finding,as TXNDC9 deficiency attenuated UV-B radiation-induced translocation of NF-κB p65 from the cytoplasm to the nucleus of cSCC.In conclusion,our work demonstrates the biological roles of TXNDC9 in cSCC progression and may provide a novel therapeutic target to treat cSCC in the future.
基金supported by the National Natural Science Foundation of China (22071172)the Ministry of Science and Technology of China (2016YFB0401100,2017YFA0204503,and 2018YFA0703200)Shandong Provincial Natural Science Foundation (No. ZR2019BB025)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically reduce CO_(2) emission and contribute to carbon-neutral cycle. E cient electrocatalytic reduction of chemically inert CO_(2) is challenging from thermodynamic and kinetic points of view. Therefore,low-cost,highly e cient,and readily available electrocatalysts have been the focus for promoting the conversion of CO_(2). Very recently,interface engineering has been considered as a highly e ective strategy to modulate the electrocatalytic performance through electronic and/or structural modulation,regulations of electron/proton/mass/intermediates,and the control of local reactant concentration,thereby achieving desirable reaction pathway,inhibiting competing hydrogen generation,breaking binding-energy scaling relations of intermediates,and promoting CO_(2) mass transfer. In this review,we aim to provide a comprehensive overview of current developments in interface engineering for CO_(2) RR from both a theoretical and experimental stand-point,involving interfaces between metal and metal,metal and metal oxide,metal and nonmetal,metal oxide and metal oxide,organic molecules and inorganic materials,electrode and electrolyte,molecular catalysts and electrode,etc. Finally,the opportunities and challenges of interface engineering for CO_(2) RR are proposed.
基金supported by the Taishan Scholar Project of Shandong Province(No.tsqn201812083)the Natural Science Foundation of Shandong Province(Nos.ZR2021JQ15,ZR2020QE071,ZR2020LLZ006,and ZR2020MH191)+1 种基金the Innovative Team Project of Jinan(No.2021GXRC019)the National Natural Science Foundation of China(Nos.52022037,52102171,and 62174068).
文摘Vapor deposition and three-dimensional(3D)printing technology are considered to be conventional methods to achieve patterned metal film preparation through the assistance of masks and high temperature.Therefore,there are still some challenges in fabricating metal films in template-free and normal temperature environment.In this work,we report a flexible and rapid laser metal transfer(LMT)technique for fabricating the various metal films(Cu,Ni,Sn,Al,Fe,and Ag)with different patterns without templates on arbitrary substrates(glass,polyimide(PI)films,and aluminum nitride(AlN)ceramic).Especially,the obtained transparent conductive glass displays high transmittance(more than 90%)and adjustable resistances(≈5Ω).According to the Joule effect,the interface resistance between Cu particles and copper oxide coating produces the high temperature approximately 280℃ at 2 V in a short time(≈60 s)and remains stable at 120℃ over 12 h.At last,the multifunctional glass with Cu patterns also shows excellent bactericidal activity(≈95%).This work demonstrates that laser metal transfer is an exceeding effective means of fabricating the micro/nano structures with potential applications in functional devices.
基金supported by Shandong Provincial Natural Science Foundation(No.ZR2019BB025)the National Natural Science Foundation of China(Nos.21976014 and U1930402)+1 种基金The Fundamental Research Funds for the Central Universities(FRFTP-20-11B and FRF-BR-20-02B)the generous computer time from TianHe2-JK Supercomputer Center。
文摘Transition metal nitride/carbide(TMN/C)have been actively explored as low-cost hydrogen evolution reaction(HER)electrocatalysts owing to their Pt-like physical and chemical properties.Unfortunately,pure TMN/C suffers from strong hydrogen adsorption and lacks active centers for water dissociation.Herein,we developed a switchable WO_(3)-based in situ gas–solid reaction for preparing sophisticated Fe-N doped WC and Fe-C doped WN nanoarrays.Interestingly,the switch of codoping and phase can be effectively manipulated by regulating the amount of ferrocene.Resultant Fe-C-WN and Fe-N-WC exhibit robust electrocatalytic performance for HER in alkaline and acid electrolytes,respectively.The collective collaboration of morphological,phase and electronic effects are suggested to be responsible for the superior HER activity.The smallest|ΔGH*|value of Fe-NWC indicates preferable hydrogen-evolving kinetics on the Fe-N-WC surface for HER under acid condition,while Fe-C-WN is suggested to be beneficial to the adsorption and dissociation of H_(2)O for HER in alkaline electrolyte.
基金supported by Shandong Provincial Natural Science Foundation (No. ZR2019BB025)。
文摘The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a sustainable and environmentally friendly energy source for human production and living.Very recently, photothermal catalysis has been proved to exhibit great advantages in reducing the reaction temperature, promoting the catalytic activity, and manipulating the reaction pathway in comparison with traditional thermal catalysis. In this review, we firstly introduced the fundamental mechanisms and categories of photothermal catalysis to understand the synergy or the difference between photochemical and thermochemical reaction pathways. Subsequently, the criteria and strategies for photothermal catalyst design are discussed in order to inspire the development of high-efficiency photothermal catalytic route by achieving intense absorption of broadband solar energy spectrum and high conversion capability of solar-to-heat. Recent progress in CO_(2)reduction achieved by photothermal catalysis was summarized in terms of production types. In the end, the future challenges and perspectives of photothermal catalytic CO_(2)reduction are presented. We hope that this review will not only deepen the understanding of photothermal catalysis, but also inspire the design, preparation and application of high-performance photothermal catalysts, aiming at alleviating non-renewable fossil energy consumption and carbon emissions for early carbon emission peak and carbon neutrality.
基金supported by the National Natural Science Foundation of China (31771292 and 31571162)。
文摘Stroke is an acute cerebro-vascular disease with high incidence and poor prognosis,most commonly ischemic in nature.In recent years,increasing attention has been paid to inflammatory reactions as symptoms of a stroke.However,the role of inflammation in stroke and its underlying mechanisms require exploration.In this study,we evaluated the inflammatory reactions induced by acute ischemia and found that pyroptosis occurred after acute ischemia both in vivo and in vitro,as determined by interleukin-1β,apoptosis-associated speck-like protein,and caspase-1.The early inflammation resulted in irreversible ischemic injury,indicating that it deserves thorough investigation.Meanwhile,acute ischemia decreased the Sirtuin 1(Sirtl)protein levels,and increased the TRAF6(TNF receptor associated factor 6)protein and reactive oxygen species(ROS)levels.In further exploration,both Sirtl suppression and TRAF6 activation were found to contribute to this pyroptosis.Reduced Sirtl levels were responsible for the production of ROS and increased TRAF6 protein levels after ischemic exposure.Moreover,N-acetyl-L-cysteine,an ROS scavenger,suppressed the TRAF6 accumulation induced by oxygen-glucose deprivation via suppression of ROS bursts.These phenomena indicate that Sirtl is upstream of ROS,and ROS bursts result in increased TRAF6 levels.Further,the activation of Sirtl during the period of ischemia reduced ischemiainduced injury after 72 h of reperfusion in mice with middle cerebral artery occlusion.In sum,these results indicate that pyroptosis-dependent machinery contributes to the neural injury during acute ischemia via the Sirt1-ROS-TRAF6 signaling pathway.We propose that inflammatory reactions occur soon after oxidative stress and are detrimental to neuronal survival;this provides a promising therapeutic target against ischemic injuries such as a stroke.
基金This work was supported by Shandong Provincial Natural Science Foundation(No.ZR2019BB025)the Project of“20 items of University”of Jinan(No.2018GXRC031).
文摘The catalytic conversion of carbon dioxide(CO_(2))into high value-added chemicals is of great significance to address the pressing carbon cycle issues.Reticular chemistry of metal-organic frameworks(MOFs)-based materials exhibits great potential and effectiveness to face CO_(2)challenge from capture to conversion.To date,the integrated nanocomposites of nanostructure and MOF have emerged as a powerful heterogeneous catalysts featured with multifold advantages including synergistic effects between the two interfaces,confinement effect of meso-and micropores,tandem reaction triggered by multiple active sites,high stability and dispersion,and so on.Given burgeoning carbon cycle and nanostructure@MOFs,this review highlights some of important advancements to provide a full understanding on the synthesis and design of nanostructure@MOFs composites to facilitate carbon cycle through CO_(2)photocatalytic,electrocatalytic,and thermal conversion.Afterward,the catalytic applications of some representative nanostructure@MOFs composites are categorized,in which the origin of activity or structure-activity relationship is summarized.Finally,the opportunities and challenges are proposed for inspiring the future development of nanostructure@MOFs composites for carbon cycle.
基金This work was supported by the National Key Research and Development Program of China(2017YFB0405400)Shandong Provincial Natural Science Foundation(ZR2019BB025,2018YFJH0503 and ZR2018ZC0842)the Joint Fund of the National Natural Science Foundation Committee of China Academy of Engineering Physics(U1530401).
基金This work was supported by the National Key Research and Development Program of China(No.2017YFB0405400)Shandong Provincial Natural Science Foundation(Nos.ZR2019BB025 and ZR2018ZC0842)+2 种基金the Project of“20 items of University”of Jinan(No.2018GXRC031)the National Natural Science Foundation of China(Nos.21976014,U1930402 and 22071172)the generous computer time from TianHe2-JK Supercomputer Center.
文摘Electrocatalytic hydrogen production in alkaline media is extensively adopted in industry. Unfortunately, further performance improvement is severely impeded by the retarded kinetics, which requires the fine regulation of water dissociation, hydrogen recombination, and hydroxyl desorption. Herein, we develop a multi-interface engineering strategy to make an elaborate balance for the alkaline hydrogen evolution reaction (HER) kinetics. The graphene cross-linked three-phase nickel sulfide (NiS-NiS_(2)-Ni_(3)S_(4)) polymorph foam (G-NNNF) was constructed through hydrothermal sulfidation of graphene wrapped nickel foam as a three-dimensional (3D) scaffold template. The G-NNNF exhibits superior catalytic activity toward HER in alkaline electrolyte, which only requires an overpotential of 68 mV to drive 10 mA·cm^(−2) and is better than most of the recently reported metal sulfides catalysts. Density functional theory (DFT) calculations verify the interfaces between nickel sulfides (NiS/NiS_(2)-Ni_(3)S_(4)) and cross-linked graphene can endow the electrocatalyst with preferable hydrogen adsorption as well as metallic nature. In addition, the electron transfer from Ni_(3)S_(4)/NiS_(2) to NiS results in the electron accumulation on NiS and the hole accumulation on Ni_(3)S_(4)/NiS_(2), respectively. The electron accumulation on NiS favors the optimization of the H* adsorption, whereas the hole accumulation on Ni_(3)S_(4) is beneficial for the adsorption of H_(2)O. The work about multi-interface collaboration pushes forward the frontier of excellent polymorph catalysts design.
基金supported by the National Natural Science Foundation of China(Nos.21907043 and 21801153)Shandong Provincial Natural Science Foundation(No.ZR2019BB025).
文摘Electroreduction of greenhouse gas CO_(2) into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change.However,the regulations of the selectivity towards C2 product and the competing hydrogen evolution reaction(HER)are major challenges for CO_(2) reduction reaction(CO_(2)RR).Here,we develop an interface-enhanced strategy by depositing a thin layer of nitrogen-doped graphene(N-G)on a Cu foam surface(Cu-N-G)to selectively promote the ethanol pathway in CO_(2)RR.Compared to the undetectable ethanol selectivity of pure Cu and Cu@graphene(Cu-G),Cu-N-G has boosted the ethanol selectivity to 33.1%in total Faradic efficiency(FE)at−0.8 V vs.reversible hydrogen electrode(RHE).The experimental and density functional theory(DFT)results verify that the interconnected graphene coating can not only serve as the fast charge transport channel but also provide confined nanospace for mass transfer.The N doping can not only trigger the intrinsic interaction between N in N-G and CO_(2) molecule for enriching the local concentration of reactants but also promote the average valence state of Cu for C–C coupling pathways.The confinement effect at the interface of Cu-N-G can not only provide high adsorbed hydrogen(Had)coverage but also stabilize the key*HCCHOH intermediate towards ethanol pathway.The provided interface-enhanced strategy herein is expected to inspire the design of Cubased CO_(2)RR electrocatalysts towards multi-carbon products.
基金supported by Shandong Provincial Natural Science Foundation (ZR2019BB025)the Project of “20 items of University” of Jinan (2018GXRC031)the National Natural Science Foundation of China (22071172)
文摘Since the advent of graphene in 2004,two-dimensional(2D)materials had ignited the development of fascinating functional materials for almost 20 years.Currently,the main members of 2D materials family are graphene,transition metal dichalcogenides(TMDs,MoS_(2),WS_(2),and others),MXenes(Ti_(3)C_(2),Ta_(4)C_(3),and others),Xenes(B,Si,P,Ge,and Sn),organic materials(COF,covalent organic frameworks),etc.The unique sheet-like morphology(single-or few-atomic-layer thickness)endow 2D materials with unconventional physicochemical properties for promising applications in catalysis,energy storage/conversion,electronics,biomedicine,sensors,etc.Nevertheless,the exploration and preparation of novel twodimensional materials with desired characteristics through highly controlled strategy remains one of the major challenges in this field.In a recent work from Nature Chemistry published on 10 February 2022,Liu et al.reported a new member,clusterphene,in the family of two-dimensional materials.
基金supported by the National Key Research and Development Program of China(No.2017YFB0405400)Shandong Provincial Natural Science Foundation(Nos.ZR2019BB025 and ZR2018ZC0842)the Project of 4"20 items of University"ofjinan(No.2018GXRC031).
文摘Spatial isolation of different functional sites at the nanoscale in multifunctional catalysts for steering reaction sequence and paths remains a major challenge.Herein,we reported the spatial separation of dual-site Au and RuO_(2)on the nanosurface of TiO_(2)(Au/TiO_(2)/RuO_(2))through the strong metal-support interaction(SMSI)and the lattice matching(LM)for robust photocatalytic hydrogen evolution.The SMSI between Au and TiO_(2)induced the encapsulation of Au nanoparticles by an impermeable TiO_(x)overlayer,which can function as a physical separation barrier to the permeation of the second precursor.The LM between RuO_(2)and rutile-TiO_(2)can increase the stability of RuO_(2)/TiO_(2)interface and thus prevent the aggregation of dual-site Au and RuO_(2)in the calcination process of removing TiO_(x)overlayer of Au.The photocatalytic hydrogen production is used as a model reaction to evaluate the performance of spatially separated dual-site Au/TiO_(2)/RuO_(2)catalysts.The rate of hydrogen production of the Au/TiO_(2)/RuO_(2)is as high as 84μmol h^(−1)g^(−1)under solar light irradiation without sacrificial agents,which is 2.5 times higher than the reference Au/TiO_(2)and non-separated Au/RuO_(2)/TiO_(2)samples.Systematic characterizations verify that the spatially separated dual-site Au and RuO_(2)on the nanosurface of TiO_(2)can effectively separate the photo-generated carriers and lower the height of the Schottky barrier,respectively,under UV and visible light irradiation.This study provides new inspiration for the precise construction of different sites in multifunctional catalysts.