The development of efficient single-atom catalysts(SACs) for the oxygen reduction reaction(ORR)remains a formidable challenge,primarily due to the symmetric charge distribution of metal singleatom sites(M-N_(4)).To ad...The development of efficient single-atom catalysts(SACs) for the oxygen reduction reaction(ORR)remains a formidable challenge,primarily due to the symmetric charge distribution of metal singleatom sites(M-N_(4)).To address such issue,herein,Fe-N_(x) sites coupled synergistic catalysts fabrication strategy is presented to break the uniform electronic distribution,thus enhancing the intrinsic catalytic activity.Precisely,atomically dispersed Fe-N_(x) sites supported on N/S-doped mesoporous carbon(NSC)coupled with FeS@C core-shell nanoparticles(FAS-NSC@950) is synthesized by a facile hydrothermal reaction and subsequent pyrolysis.Due to the presence of an in situ-grown conductive graphitic layer(shell),the FeS nanoparticles(core) effectively adjust the electronic structure of single-atom Fe sites and facilitate the ORR kinetics via short/long-range coupling interactions.Consequently,FAS-NSC@950displays a more positive half-wave potential(E_(1/2)) of 0.871 V with a significantly boosted ORR kinetics(Tafel slope=52.2 mV dec^(-1)),outpacing the commercial Pt/C(E_(1/2)=0.84 V and Tafel slope=54.6 mV dec^(-1)).As a bifunctional electrocatalyst,it displays a smaller bifunctional activity parameter(ΔE) of 0.673 V,surpassing the Pt/C-RuO_(2) combination(ΔE=0.724 V).Besides,the FAS-NSC@950-based zincair battery(ZAB) displays superior power density,specific capacity,and long-term cycling performance to the Pt/C-Ir/C-based ZAB.This work significantly contributes to the field by offering a promising strategy to enhance the catalytic activity of SACs for ORR,with potential implications for energy conversion and storage technologies.展开更多
Binder-free bifunctional electrocatalysts are attractive for rechargeable Zn-air batteries(ZABs)in gridscale energy storage and flexible electronics,but suffering from the sluggish mass transport and inadequate cataly...Binder-free bifunctional electrocatalysts are attractive for rechargeable Zn-air batteries(ZABs)in gridscale energy storage and flexible electronics,but suffering from the sluggish mass transport and inadequate catalytic capability.Herein,we propose a scalable approach of in-situ engineering highly exposed Fe-N_(4)/Cxsites on the N,S-doped porous carbon nanofiber membrane as a binder-free air electrode catalyst for ZABs.ZnS nanospheres are firstly used as integrated structure-directing agents to facilitate the electronic modulation of Fe-N_(4)/Cxsites by S doping and construct the hierarchical macro/meso/micropores at high temperature.Neither additional step for removal of ZnS nanospheres nor doping process is required,significantly simplifying the pore formation process and improving the S doping efficiency.Benefiting from the enhanced intrinsic activity of high-density Fe-N_(4)/Cxsites(23.53μmol g^(-1))and the optimized mass transport of carbon nanofibers,as-synthesized electrocatalyst shows a positive half-wave potential of 0.89 V for oxygen reduction reaction and a small overpotential of 0.47 V at 10 m A cm^(-2)for oxygen evolution reaction.When used as the air cathode catalyst for ZABs,it delivers a high specific capacity of 699 m Ah g^(-1)at 5 m A cm^(-2),a large peak power density of 228 m W cm^(-2)and a prolonged cycling over 1000 h.At 10 m A cm^(-2),a robust structure with atomically dispersed Fe is also remained after cycling for 420 h.Due to the flexible properties of the electrocatalyst,as-assembled quasi-solid-state ZAB shows stable cycling over 90 h at alternately flat/bent states,demonstrating great prospects in flexible electronic device applications.展开更多
Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their a...Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.展开更多
The active sites of samarium orthovanadate(SmVO 4) were studied by means of ESR, NO TPD and temperature programmed 18 O 2 isotope exchange(TPIE) methods. The results of ESR and NO TPD confirm the presenc...The active sites of samarium orthovanadate(SmVO 4) were studied by means of ESR, NO TPD and temperature programmed 18 O 2 isotope exchange(TPIE) methods. The results of ESR and NO TPD confirm the presence of V 4+ in the catalyst. The TPIE revealed that the 18 O 2 isotope exchange was carried out through a single exchange procedure. The V 4+ species associated with oxygen vacancies are the sites for O 2 activation.展开更多
Regulating the local coordination of Fe active center can further improve the oxygen reduction reaction(ORR)performance of Fe-N-C catalyst to meet the practical application requirements of zinc-air batteries(ZABs).Her...Regulating the local coordination of Fe active center can further improve the oxygen reduction reaction(ORR)performance of Fe-N-C catalyst to meet the practical application requirements of zinc-air batteries(ZABs).Herein,carbon vacancies modified hollow porous catalysts(C-FeZ8@PDA-950)are constructed by microenvironment modulation,achieving the efficient utilization of active sites and optimization of elec-tronic structure.Density functional theory(DFT)calculations confirm that the defective-edge Fe-N_(4) sites can weaken the adsorption free energy of OH^(∗),and hinder the dissolution of Fe center,significantly accel-erating the ORR process for ZABs.The rechargeable liquid ZABs equipped with C-FeZ8@PDA-950 display high specific capacity(819.95 mAh g Zn^(−1))and excellent long-cycling life(over 500 h).Furthermore,the relevant flexible all-solid-state ZABs also display outstanding folding performance under various bending angles.This work will provide insights into optimizing the electronic structure to improve electrocatalytic performance in the energy conversion and storage area.展开更多
Photocatalytic hydrogen evolution is an attractive fi eld for future environment-friendly energy.However,fast recombination of photogenerated charges severely inhibits hydrogen effi ciency.Single-atom cocatalysts such...Photocatalytic hydrogen evolution is an attractive fi eld for future environment-friendly energy.However,fast recombination of photogenerated charges severely inhibits hydrogen effi ciency.Single-atom cocatalysts such as Pt have emerged as an eff ective method to enhance the photocatalytic activity by introduction of active sites and boosting charge separation with low-coordination environment.Herein,we demonstrated a new strategy to develop a highly active Pd single atom in carbondefi cient g-C_(3)N_(4)with a unique coordination.The single-atom Pd–N_(3)sites constructed by oil bath heating and photoreduction process were confi rmed by HADDF-STEM and XPS measurements.Introduction of single-atom Pd greatly improved the separation and transportation of charge carriers,leading to a longer lifespan for consequent reactions.The obtained singleatom Pd loaded on the carbon-defi cient g-C_(3)N_(4)showed excellent photocatalytic activity in hydrogen production with about 24 and 4 times higher activity than that of g-C_(3)N_(4)and nano-sized Pd on the same support,respectively.This work provides a new insight on the design of single-atom catalyst.展开更多
Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored ...Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored in porous nanomaterials is still challenging.Here,through the template-free S-assisted pyrolysis of low-cost Fe-salts with melamine(MA),porous alveolate Fe/g-C3N4 catalysts with high-density(Fe loading up to 17.7 wt%)and increased USCAD Fe sites were synthesized.The presence of a certain amount of S species in the Fe-salts/MA system plays an important role in the formation of USCAD S-Fe-salt/CN catalysts;the S species act as a"sacrificial carrier"to increase the dispersion of Fe species through Fe-S coordination and generate porous alveolate structure by escaping in the form of SO2 during pyrolysis.The S-Fe-salt/CN catalysts exhibit greatly promoted activity and reusability for degrading various organic pollutants in advanced oxidation processes compared to the corresponding Fe-salt/CN catalysts,due to the promoted accessibility of USCAD Fe sites by the porous alveolate structure.This S-assisted method exhibits good feasibility in a large variety of S species(thiourea,S powder,and NH4SCN)and Fe salts,providing a new avenue for the low-cost and large-scale synthesis of high-density USCAD metal/g-C3N4 catalysts.展开更多
Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordinati...Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordination number of N atoms bonded with central metal.Herein,we develop a family of single metal atom bonded by N atoms anchored on carbons(SAs-M-N-C,M=Fe,Co,Ni,Cu)for CO2 ER,which composed of accurate pyrrole-type M-N4 structures with isolated metal atom coordinated by four pyrrolic N atoms.Benefitting from atomically coordinated environment and specific selectivity of M-N4 centers,SAs-Ni-N-C exhibits superior CO2 ER performance with onset potential of-0.3 V,CO Faradaic efficiency(F.E.) of 98.5%at-0.7 V,along with low Tafel slope of 115 mV dec-1 and superior stability of 50 h,exceeding all the previously reported M-N-C electrocatalysts for CO2-to-CO conversion.Experimental results manifest that the different intrinsic activities of M-N4 structures in SAs-M-N-C result in the corresponding sequence of Ni> Fe> Cu> Co for CO2 ER performance.An integrated Zn-CO2 battery with Zn foil and SAs-Ni-N-C is constructed to simultaneously achieve CO2-to-CO conversion and electric energy output,which delivers a peak power density of 1.4 mW cm-2 and maximum CO F.E.of 93.3%.展开更多
The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction wa...The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.展开更多
目的:探究胃癌根治术后手术部位感染(surgical site infection,SSI)影响因素及血清单核细胞趋化蛋白-1(monocyte chemoattractant protein-1,MCP1)、糖类抗原72-4(carbohydrate antigen 72-4,CA72-4)、可溶性白细胞分化抗原-14(soluble ...目的:探究胃癌根治术后手术部位感染(surgical site infection,SSI)影响因素及血清单核细胞趋化蛋白-1(monocyte chemoattractant protein-1,MCP1)、糖类抗原72-4(carbohydrate antigen 72-4,CA72-4)、可溶性白细胞分化抗原-14(soluble cluster of differentiation antigen-14,sCD14)水平变化意义。方法:选取2017年02月至2021年01月我院150例行胃癌根治术患者作为研究对象,根据患者术后是否出现SSI分为两组,感染组(n=35)与非感染组(n=115)。比较两组患者临床资料、手术前后血清MCP1、CA72-4、sCD14水平,分析胃癌根治术后SSI影响因素。绘制受试者工作特征曲线(receiver operating characteristic curve,ROC),评价胃癌根治术后血清MCP1、CA72-4、sCD14水平对SSI的诊断价值。分析术后血清MCP1、CA72-4、sCD14水平与感染程度(IPS评分)的相关性。比较术后血清MCP1、CA72-4、sCD14高水平与低水平患者病死率。结果:两组患者年龄、手术方式、临床分期、手术时间、糖尿病情况比较,差异有统计学意义(P<0.05)。感染组术后血清MCP1、CA72-4、sCD14水平高于非感染组(P<0.05)。Logistic回归方程结果显示,年龄、临床分期、糖尿病、手术方式、手术时间及术后血清MCP1、CA72-4、sCD14水平均为胃癌根治术后SSI的独立危险因素(P<0.05)。绘制胃癌根治术后血清MCP1、CA72-4、sCD14水平对SSI诊断价值的ROC曲线,结果显示胃癌根治术后血清MCP1、CA72-4、sCD14水平诊断SSI的曲线下面积(area under the curve,AUC)分别为0.804、0.768、0.777。应用Logistic二元回归拟合,构建各指标联合诊断的AUC,结果显示,联合检测的AUC为0.912。胃癌根治术后SSI患者IPS评分为(13.89±6.52)分。Pearson相关性分析可知,胃癌根治术后SSI患者血清MCP1、CA72-4、sCD14水平与感染程度呈正相关关系(P<0.05)。根据术后血清MCP1、CA72-4、sCD14水平分为高水平组与低水平组,术后血清MCP1、CA72-4、sCD14高水平组病死率明显高于低水平组,差异有统计学意义(P<0.05)。结论:胃癌根治术后SSI发病影响因素包括年龄、临床分期、糖尿病、手术方式、手术时间及术后血清MCP1、CA72-4、sCD14水平,且临床检测术后血清MCP1、CA72-4、sCD14水平,在SSI诊断、病情评估及预后预测中具有重要价值。展开更多
Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subje...Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subjected to atomic-level structural engineering by doping with transition metals(M=Fe,Co,or Ni),which simultaneously induced the formation of metal-N active sites in the g-C_(3)N_(4)framework and modulated the bandgap of g-C_(3)N_(4).Experiments and density functional theory calculations further verified that the as-formed metal-N bonds in M-doped g-C_(3)N_(4)acted as an"electron transfer bridge",where the migration of photo-generated electrons along the bridge enhanced the efficiency of separation of the photogenerated charges,and the optimized bandgap of g-C_(3)N_(4)afforded stronger reduction ability and wider light absorption.As a result,doping with either Fe,Co,or Ni had a positive effect on the HER activity,where Co-doped g-C_(3)N_(4)exhibited the highest performance.The findings illustrate that this atomic-level structural engineering could efficiently improve the HER activity and inspire the design of powerful photocatalysts.展开更多
At Kuwana illegal dumping site in Japan, where hazardous waste was illegally dumped, groundwater was severely contaminated by Volatile Organic Compounds (VOCs). Groundwater was already remedied by conducting Pump-and-...At Kuwana illegal dumping site in Japan, where hazardous waste was illegally dumped, groundwater was severely contaminated by Volatile Organic Compounds (VOCs). Groundwater was already remedied by conducting Pump-and-Treat (P&T) after containment of all the waste by vertical slurry walls from 2002 to 2007. However, 1,4-dioxane was detected in both waste and groundwater outside of slurry walls after it was newly added into Japan environmental standards in late 2009, which suggested that the walls did not contain 1,4-dioxane completely. Our previous study developed a model to predict the 1,4-dioxane distribution in groundwater after the previous remediation at the site. In this study, numerical simulation was applied for remediation planning at the site based on the concept of Verified Follow Up (VF-UP) that had been proposed as a new approach to complete remediation effectively with consideration of future risks. The amount of waste to be removed and pumping plans were discussed by numerical simulation to achieve the remedial objective in which 1,4-dioxane in groundwater outside of walls is remedied within 10 years and 1,4-dioxane spreading throughout the walls is prevented in the case where a portion of waste is remained. Firstly, the amount of waste to be removed considering pumping plans for P&T was determined by scenario analysis. As a result, at least two-third of waste should be removed by combining with P&T. However, if the waste is remained, future risks of 1,4-dioxane spreading through the slurry walls may occur. Our simulation suggested that groundwater within the remaining waste must be pumped up at least 20 m3/d for containment of 1,4-dioxane within the remaining waste. In conclusion, our numerical simulation determined the amount of waste to be removed and the pumping plans for P&T to achieve the remedial objective effectively considering future risks based on the concept of VF-UP.展开更多
Compound(Ph_4P)[V_3MP_6](MPH_2=o-HOC_6H_4SH)was obtained by reaction of VCl_3 and Na_2MP in ethanol in the presence of Ph_4PBr.It is triclinic and crystallizes in space group P1,fw=1237.3,a=14.127(4), b=14.342(4),c=15...Compound(Ph_4P)[V_3MP_6](MPH_2=o-HOC_6H_4SH)was obtained by reaction of VCl_3 and Na_2MP in ethanol in the presence of Ph_4PBr.It is triclinic and crystallizes in space group P1,fw=1237.3,a=14.127(4), b=14.342(4),c=15.878(4);α=65.08(2),β=73.09(2),T=78.68(2)°;V=2781.3~3, Z=2,d_c=1.48 g/cm^3.Final R factor is 0.063.The three vanadium atoms are linearly arranged and bridged by the oxygen atoms and terminally chelated by the thiolato-atoms of the six MP^2-ligands in pseudo-S_6 symmetry.展开更多
BACKGROUND Gastric cancer(GC)is the second most common cause of cancer-related deaths worldwide.Hepatocyte nuclear factor 4 alpha(HNF4α)that belongs to the nuclear hormone receptor superfamily,is overexpressed in GC ...BACKGROUND Gastric cancer(GC)is the second most common cause of cancer-related deaths worldwide.Hepatocyte nuclear factor 4 alpha(HNF4α)that belongs to the nuclear hormone receptor superfamily,is overexpressed in GC tissues,and might be involved in the development of GC by regulating its downstream winglessrelated integration site(WNT)/β-catenin signaling.AIM To clarify the expression of HNF4α/WNT5a/β-catenin signaling proteins in clinical GC tissues.METHODS We immunohistochemically stained pathological blocks of GC and matched paracancerous tissues.The intensity of HNF4α,WNT5a andβ-catenin staining in the tumor cells was determined according to cell rates and staining intensity.The correlations between GC and HNF4α,WNT5a,andβ-catenin expression using chisquare and paired chi-square tests.Relationships between double-positive HNF4αand WNT5a expression and types of gastric tumor tissues were assessed using regression analysis.Correlations between HNF4αand WNT5a expression at the RNA level in GC tissues found in the TCGA database were analyzed using Pearson correlation coefficients.RESULTS We found more abundant HNF4αand WNT5a proteins in GC,especially in mucinous adenocarcinoma and mixed GC than in adjacent tissues(P<0.001).Low and high levels of cytoplasmicβ-catenin respectively expressed in GC and adjacent tissues(P<0.001)were not significantly associated with pathological parameters.CONCLUSION The expressions of HNF4αand WNT5a could serve as early diagnostic biomarkers for GC.展开更多
基金financially supported by the National Natural Science Foundation of China(21773024)the Natural Science Foundation of Sichuan Province of China(2023NSFC0084)the China Postdoctoral Science Foundation(2019M663469)。
文摘The development of efficient single-atom catalysts(SACs) for the oxygen reduction reaction(ORR)remains a formidable challenge,primarily due to the symmetric charge distribution of metal singleatom sites(M-N_(4)).To address such issue,herein,Fe-N_(x) sites coupled synergistic catalysts fabrication strategy is presented to break the uniform electronic distribution,thus enhancing the intrinsic catalytic activity.Precisely,atomically dispersed Fe-N_(x) sites supported on N/S-doped mesoporous carbon(NSC)coupled with FeS@C core-shell nanoparticles(FAS-NSC@950) is synthesized by a facile hydrothermal reaction and subsequent pyrolysis.Due to the presence of an in situ-grown conductive graphitic layer(shell),the FeS nanoparticles(core) effectively adjust the electronic structure of single-atom Fe sites and facilitate the ORR kinetics via short/long-range coupling interactions.Consequently,FAS-NSC@950displays a more positive half-wave potential(E_(1/2)) of 0.871 V with a significantly boosted ORR kinetics(Tafel slope=52.2 mV dec^(-1)),outpacing the commercial Pt/C(E_(1/2)=0.84 V and Tafel slope=54.6 mV dec^(-1)).As a bifunctional electrocatalyst,it displays a smaller bifunctional activity parameter(ΔE) of 0.673 V,surpassing the Pt/C-RuO_(2) combination(ΔE=0.724 V).Besides,the FAS-NSC@950-based zincair battery(ZAB) displays superior power density,specific capacity,and long-term cycling performance to the Pt/C-Ir/C-based ZAB.This work significantly contributes to the field by offering a promising strategy to enhance the catalytic activity of SACs for ORR,with potential implications for energy conversion and storage technologies.
基金the financial support from the National Natural Science Foundation of China(51972191,52172047)the National Key Research and Development Program of China(2021YFA1200800)。
文摘Binder-free bifunctional electrocatalysts are attractive for rechargeable Zn-air batteries(ZABs)in gridscale energy storage and flexible electronics,but suffering from the sluggish mass transport and inadequate catalytic capability.Herein,we propose a scalable approach of in-situ engineering highly exposed Fe-N_(4)/Cxsites on the N,S-doped porous carbon nanofiber membrane as a binder-free air electrode catalyst for ZABs.ZnS nanospheres are firstly used as integrated structure-directing agents to facilitate the electronic modulation of Fe-N_(4)/Cxsites by S doping and construct the hierarchical macro/meso/micropores at high temperature.Neither additional step for removal of ZnS nanospheres nor doping process is required,significantly simplifying the pore formation process and improving the S doping efficiency.Benefiting from the enhanced intrinsic activity of high-density Fe-N_(4)/Cxsites(23.53μmol g^(-1))and the optimized mass transport of carbon nanofibers,as-synthesized electrocatalyst shows a positive half-wave potential of 0.89 V for oxygen reduction reaction and a small overpotential of 0.47 V at 10 m A cm^(-2)for oxygen evolution reaction.When used as the air cathode catalyst for ZABs,it delivers a high specific capacity of 699 m Ah g^(-1)at 5 m A cm^(-2),a large peak power density of 228 m W cm^(-2)and a prolonged cycling over 1000 h.At 10 m A cm^(-2),a robust structure with atomically dispersed Fe is also remained after cycling for 420 h.Due to the flexible properties of the electrocatalyst,as-assembled quasi-solid-state ZAB shows stable cycling over 90 h at alternately flat/bent states,demonstrating great prospects in flexible electronic device applications.
基金financial support from the National Natural Science Foundation of China(21878270,21878267,21922811,21978258 and 21961160742)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)+3 种基金the Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Fundamental Research Funds for the Central Universities(2020XZZX002-09)the Startup Foundation for Hundred-Talent Program of Zhejiang Universitythe Zhejiang Key Laboratory of Marine Materials and Protective Technologies(2020K10)。
文摘Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.
文摘The active sites of samarium orthovanadate(SmVO 4) were studied by means of ESR, NO TPD and temperature programmed 18 O 2 isotope exchange(TPIE) methods. The results of ESR and NO TPD confirm the presence of V 4+ in the catalyst. The TPIE revealed that the 18 O 2 isotope exchange was carried out through a single exchange procedure. The V 4+ species associated with oxygen vacancies are the sites for O 2 activation.
基金supported by the National Natural Science Foundation of China(Nos.22078028,21978026,22209016)the International Scientific and Technological Cooperation Program of Changzhou(No.CZ20220028)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_3025).
文摘Regulating the local coordination of Fe active center can further improve the oxygen reduction reaction(ORR)performance of Fe-N-C catalyst to meet the practical application requirements of zinc-air batteries(ZABs).Herein,carbon vacancies modified hollow porous catalysts(C-FeZ8@PDA-950)are constructed by microenvironment modulation,achieving the efficient utilization of active sites and optimization of elec-tronic structure.Density functional theory(DFT)calculations confirm that the defective-edge Fe-N_(4) sites can weaken the adsorption free energy of OH^(∗),and hinder the dissolution of Fe center,significantly accel-erating the ORR process for ZABs.The rechargeable liquid ZABs equipped with C-FeZ8@PDA-950 display high specific capacity(819.95 mAh g Zn^(−1))and excellent long-cycling life(over 500 h).Furthermore,the relevant flexible all-solid-state ZABs also display outstanding folding performance under various bending angles.This work will provide insights into optimizing the electronic structure to improve electrocatalytic performance in the energy conversion and storage area.
基金This work was supported by the National Natural Science Foundation of China(Nos.21976116,21473248)Guangdong Science and Technology Program(No.2018A050506025)+3 种基金Guangzhou Science and Technology Program(Nos.202002030406,201804010181)High Level Talents Introduction Project of"Pearl River Talent Plan"in Guangdong Province(No.2019CX01L308)the Support Scheme of Guangzhou for Leading Talents in Innovation and Entrepreneurship Funding(No.2016015)the Key Deployment Projects of Chinese Academy of Sciences(No.ZDRW_CN_2020_1).
文摘Photocatalytic hydrogen evolution is an attractive fi eld for future environment-friendly energy.However,fast recombination of photogenerated charges severely inhibits hydrogen effi ciency.Single-atom cocatalysts such as Pt have emerged as an eff ective method to enhance the photocatalytic activity by introduction of active sites and boosting charge separation with low-coordination environment.Herein,we demonstrated a new strategy to develop a highly active Pd single atom in carbondefi cient g-C_(3)N_(4)with a unique coordination.The single-atom Pd–N_(3)sites constructed by oil bath heating and photoreduction process were confi rmed by HADDF-STEM and XPS measurements.Introduction of single-atom Pd greatly improved the separation and transportation of charge carriers,leading to a longer lifespan for consequent reactions.The obtained singleatom Pd loaded on the carbon-defi cient g-C_(3)N_(4)showed excellent photocatalytic activity in hydrogen production with about 24 and 4 times higher activity than that of g-C_(3)N_(4)and nano-sized Pd on the same support,respectively.This work provides a new insight on the design of single-atom catalyst.
文摘Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored in porous nanomaterials is still challenging.Here,through the template-free S-assisted pyrolysis of low-cost Fe-salts with melamine(MA),porous alveolate Fe/g-C3N4 catalysts with high-density(Fe loading up to 17.7 wt%)and increased USCAD Fe sites were synthesized.The presence of a certain amount of S species in the Fe-salts/MA system plays an important role in the formation of USCAD S-Fe-salt/CN catalysts;the S species act as a"sacrificial carrier"to increase the dispersion of Fe species through Fe-S coordination and generate porous alveolate structure by escaping in the form of SO2 during pyrolysis.The S-Fe-salt/CN catalysts exhibit greatly promoted activity and reusability for degrading various organic pollutants in advanced oxidation processes compared to the corresponding Fe-salt/CN catalysts,due to the promoted accessibility of USCAD Fe sites by the porous alveolate structure.This S-assisted method exhibits good feasibility in a large variety of S species(thiourea,S powder,and NH4SCN)and Fe salts,providing a new avenue for the low-cost and large-scale synthesis of high-density USCAD metal/g-C3N4 catalysts.
基金financial support from Zhejiang Province Basic Public Welfare Research Project(LGF19B070006)financial supports from National Natural Science Foundation of China(21922811,21878270,51702284,21961160742)+2 种基金Zhejiang Provincial Natural Science Foundation of China(LR19B060002)supported by the Fundamental Research Funds for the Central Universitiesthe Startup Foundation for Hundred-Talent Program of Zhejiang University.
文摘Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordination number of N atoms bonded with central metal.Herein,we develop a family of single metal atom bonded by N atoms anchored on carbons(SAs-M-N-C,M=Fe,Co,Ni,Cu)for CO2 ER,which composed of accurate pyrrole-type M-N4 structures with isolated metal atom coordinated by four pyrrolic N atoms.Benefitting from atomically coordinated environment and specific selectivity of M-N4 centers,SAs-Ni-N-C exhibits superior CO2 ER performance with onset potential of-0.3 V,CO Faradaic efficiency(F.E.) of 98.5%at-0.7 V,along with low Tafel slope of 115 mV dec-1 and superior stability of 50 h,exceeding all the previously reported M-N-C electrocatalysts for CO2-to-CO conversion.Experimental results manifest that the different intrinsic activities of M-N4 structures in SAs-M-N-C result in the corresponding sequence of Ni> Fe> Cu> Co for CO2 ER performance.An integrated Zn-CO2 battery with Zn foil and SAs-Ni-N-C is constructed to simultaneously achieve CO2-to-CO conversion and electric energy output,which delivers a peak power density of 1.4 mW cm-2 and maximum CO F.E.of 93.3%.
基金supported by National Natural Science Foundation of China(22369022)Technology Innovation Leading Program of Shaanxi(2022QFY07-03)。
文摘The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.
文摘目的:探究胃癌根治术后手术部位感染(surgical site infection,SSI)影响因素及血清单核细胞趋化蛋白-1(monocyte chemoattractant protein-1,MCP1)、糖类抗原72-4(carbohydrate antigen 72-4,CA72-4)、可溶性白细胞分化抗原-14(soluble cluster of differentiation antigen-14,sCD14)水平变化意义。方法:选取2017年02月至2021年01月我院150例行胃癌根治术患者作为研究对象,根据患者术后是否出现SSI分为两组,感染组(n=35)与非感染组(n=115)。比较两组患者临床资料、手术前后血清MCP1、CA72-4、sCD14水平,分析胃癌根治术后SSI影响因素。绘制受试者工作特征曲线(receiver operating characteristic curve,ROC),评价胃癌根治术后血清MCP1、CA72-4、sCD14水平对SSI的诊断价值。分析术后血清MCP1、CA72-4、sCD14水平与感染程度(IPS评分)的相关性。比较术后血清MCP1、CA72-4、sCD14高水平与低水平患者病死率。结果:两组患者年龄、手术方式、临床分期、手术时间、糖尿病情况比较,差异有统计学意义(P<0.05)。感染组术后血清MCP1、CA72-4、sCD14水平高于非感染组(P<0.05)。Logistic回归方程结果显示,年龄、临床分期、糖尿病、手术方式、手术时间及术后血清MCP1、CA72-4、sCD14水平均为胃癌根治术后SSI的独立危险因素(P<0.05)。绘制胃癌根治术后血清MCP1、CA72-4、sCD14水平对SSI诊断价值的ROC曲线,结果显示胃癌根治术后血清MCP1、CA72-4、sCD14水平诊断SSI的曲线下面积(area under the curve,AUC)分别为0.804、0.768、0.777。应用Logistic二元回归拟合,构建各指标联合诊断的AUC,结果显示,联合检测的AUC为0.912。胃癌根治术后SSI患者IPS评分为(13.89±6.52)分。Pearson相关性分析可知,胃癌根治术后SSI患者血清MCP1、CA72-4、sCD14水平与感染程度呈正相关关系(P<0.05)。根据术后血清MCP1、CA72-4、sCD14水平分为高水平组与低水平组,术后血清MCP1、CA72-4、sCD14高水平组病死率明显高于低水平组,差异有统计学意义(P<0.05)。结论:胃癌根治术后SSI发病影响因素包括年龄、临床分期、糖尿病、手术方式、手术时间及术后血清MCP1、CA72-4、sCD14水平,且临床检测术后血清MCP1、CA72-4、sCD14水平,在SSI诊断、病情评估及预后预测中具有重要价值。
文摘Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subjected to atomic-level structural engineering by doping with transition metals(M=Fe,Co,or Ni),which simultaneously induced the formation of metal-N active sites in the g-C_(3)N_(4)framework and modulated the bandgap of g-C_(3)N_(4).Experiments and density functional theory calculations further verified that the as-formed metal-N bonds in M-doped g-C_(3)N_(4)acted as an"electron transfer bridge",where the migration of photo-generated electrons along the bridge enhanced the efficiency of separation of the photogenerated charges,and the optimized bandgap of g-C_(3)N_(4)afforded stronger reduction ability and wider light absorption.As a result,doping with either Fe,Co,or Ni had a positive effect on the HER activity,where Co-doped g-C_(3)N_(4)exhibited the highest performance.The findings illustrate that this atomic-level structural engineering could efficiently improve the HER activity and inspire the design of powerful photocatalysts.
文摘At Kuwana illegal dumping site in Japan, where hazardous waste was illegally dumped, groundwater was severely contaminated by Volatile Organic Compounds (VOCs). Groundwater was already remedied by conducting Pump-and-Treat (P&T) after containment of all the waste by vertical slurry walls from 2002 to 2007. However, 1,4-dioxane was detected in both waste and groundwater outside of slurry walls after it was newly added into Japan environmental standards in late 2009, which suggested that the walls did not contain 1,4-dioxane completely. Our previous study developed a model to predict the 1,4-dioxane distribution in groundwater after the previous remediation at the site. In this study, numerical simulation was applied for remediation planning at the site based on the concept of Verified Follow Up (VF-UP) that had been proposed as a new approach to complete remediation effectively with consideration of future risks. The amount of waste to be removed and pumping plans were discussed by numerical simulation to achieve the remedial objective in which 1,4-dioxane in groundwater outside of walls is remedied within 10 years and 1,4-dioxane spreading throughout the walls is prevented in the case where a portion of waste is remained. Firstly, the amount of waste to be removed considering pumping plans for P&T was determined by scenario analysis. As a result, at least two-third of waste should be removed by combining with P&T. However, if the waste is remained, future risks of 1,4-dioxane spreading through the slurry walls may occur. Our simulation suggested that groundwater within the remaining waste must be pumped up at least 20 m3/d for containment of 1,4-dioxane within the remaining waste. In conclusion, our numerical simulation determined the amount of waste to be removed and the pumping plans for P&T to achieve the remedial objective effectively considering future risks based on the concept of VF-UP.
文摘Compound(Ph_4P)[V_3MP_6](MPH_2=o-HOC_6H_4SH)was obtained by reaction of VCl_3 and Na_2MP in ethanol in the presence of Ph_4PBr.It is triclinic and crystallizes in space group P1,fw=1237.3,a=14.127(4), b=14.342(4),c=15.878(4);α=65.08(2),β=73.09(2),T=78.68(2)°;V=2781.3~3, Z=2,d_c=1.48 g/cm^3.Final R factor is 0.063.The three vanadium atoms are linearly arranged and bridged by the oxygen atoms and terminally chelated by the thiolato-atoms of the six MP^2-ligands in pseudo-S_6 symmetry.
基金Supported by National Natural Science Foundation of China,No.81673757.
文摘BACKGROUND Gastric cancer(GC)is the second most common cause of cancer-related deaths worldwide.Hepatocyte nuclear factor 4 alpha(HNF4α)that belongs to the nuclear hormone receptor superfamily,is overexpressed in GC tissues,and might be involved in the development of GC by regulating its downstream winglessrelated integration site(WNT)/β-catenin signaling.AIM To clarify the expression of HNF4α/WNT5a/β-catenin signaling proteins in clinical GC tissues.METHODS We immunohistochemically stained pathological blocks of GC and matched paracancerous tissues.The intensity of HNF4α,WNT5a andβ-catenin staining in the tumor cells was determined according to cell rates and staining intensity.The correlations between GC and HNF4α,WNT5a,andβ-catenin expression using chisquare and paired chi-square tests.Relationships between double-positive HNF4αand WNT5a expression and types of gastric tumor tissues were assessed using regression analysis.Correlations between HNF4αand WNT5a expression at the RNA level in GC tissues found in the TCGA database were analyzed using Pearson correlation coefficients.RESULTS We found more abundant HNF4αand WNT5a proteins in GC,especially in mucinous adenocarcinoma and mixed GC than in adjacent tissues(P<0.001).Low and high levels of cytoplasmicβ-catenin respectively expressed in GC and adjacent tissues(P<0.001)were not significantly associated with pathological parameters.CONCLUSION The expressions of HNF4αand WNT5a could serve as early diagnostic biomarkers for GC.
