We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in...We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in S_(v)–In_(2)S_(3)@2H–MoTe_(2).The X-ray absorption near-edge structure shows that the formation of S_(v)–In_(2)S_(3)@2H–MoTe_(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface.The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption,time-resolved,and in situ diffuse reflectance–Infrared Fourier transform spectroscopy.A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S_(v)–In_(2)S_(3)@2H–MoTe_(2)(5)photogenerated carrier concentration relative to pristine S_(v)–In_(2)S_(3).Benefiting from lower carrier transport activation energy,an internal quantum efficiency of 94.01%at 380 nm was used for photocatalytic CO_(2)RR.This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO_(2)RR.展开更多
Spontaneous imbibition(SI)is an important mechanism for enhancing oil recovery in low-permeability reservoirs.Due to the strong heterogeneity,and the non-Darcy flow,the construction of SI model for lowpermeability res...Spontaneous imbibition(SI)is an important mechanism for enhancing oil recovery in low-permeability reservoirs.Due to the strong heterogeneity,and the non-Darcy flow,the construction of SI model for lowpermeability reservoirs is extremely challenging.Commonly,traditional SI models based on single or averaged capillary tortuosity ignore the influence of heterogeneity of pore seepage channels and the threshold pressure(TP)on imbibition.Therefore,in this work,based on capillary model and fractal theory,a mathematical model of characterizing SI considering heterogeneity of pore seepage channels is established.On this basis,the threshold pressure was introduced to determine the pore radius at which the wetted phase can displace oil.The proposed new SI model was verified by imbibition experimental data.The study shows that for weakly heterogeneous cores with permeability of 0-1 m D,the traditional SI model can characterize the imbibition process relatively accurately,and the new imbibition model can increase the coefficient of determination by 1.05 times.However,traditional model has serious deviations in predicting the imbibition recovery for cores with permeability of 10-50 m D.The new SI model coupling with heterogeneity of pore seepage channels and threshold pressure effectively solves this problem,and the determination coefficient is increased from 0.344 to 0.922,which is increased by2.68 times.For low-permeability reservoirs,the production of the oil in transitional pores(0.01-0.1μm)and mesopores(0.1-1μm)significantly affects the imbibition recovery,as the research shows that when the heterogeneity of pore seepage channels is ignored,the oil recovery in transitional pores and mesopores decreases by 7.54%and 4.26%,respectively.Sensitivity analysis shows that increasing interfacial tension,decreasing contact angle,oil-water viscosity ratio and threshold pressure will increase imbibition recovery.In addition,there are critical values for the influence of these factors on the imbibition recovery,which provides theoretical support for surfactant optimization.展开更多
Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of ...Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes(ZMAs)severely restrict their applications.To address these issues,we design the asymmetric Zn-N_(4) atomic sites embedded hollow fibers(AS-IHF)as the flexible host for stable ZMAs.Through introducing different nitrogen resources in the synthesis,two kinds of coordination,i,e.Zn-N(pyridinic)and Zn-N(pyrrolic),are introduced in the Zn-N_(4) atomic module synchronously.The asymmetric Zn-N_(4) module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption.Meanwhile,the highly porous structure of the hollow fiber effectively reduces local current density,homogenize Zn ion flux,and alleviate structure stress.All the advantages endow the high efficiency and good stability for Zn plating/stripping.Both theoretical and experimental results demonstrate the high reversibility,low nucleation overpotential,and dendritefree behavior of the AS-IHF@Zn anode,which afford the high stability in high-rate and long-term cycling.Moreover,the solid-state Zn-ion hybrid capacitor(ZIHC)based on AS-IHF@Zn anode shows the high flexibility,reliability,and superior long-term cycling capability in a wide-range of temperatures(-20-25℃).Therefore,the present work not only gives a new strategy for modulating local environments of single atomic sites,but also propels the development of flexible power sources for diverse electronics.展开更多
CO_(2) flooding is a vital development method for enhanced oil recovery in low-permeability reservoirs,However,micro-fractures are developed in low-permeability reservoirs,which are essential oil flow channels but can...CO_(2) flooding is a vital development method for enhanced oil recovery in low-permeability reservoirs,However,micro-fractures are developed in low-permeability reservoirs,which are essential oil flow channels but can also cause severe CO_(2) gas channeling problems.Therefore,anti-gas channeling is a necessary measure to improve the effect of CO_(2) flooding.The kind of anti-gas channeling refers to the plugging of fractures in the deep formation to prevent CO_(2) gas channeling,which is different from the wellbore leakage.Polymer microspheres have the characteristics of controllable deep plugging,which can achieve the profile control of low-permeability fractured reservoirs.In acidic environments with supercritical CO_(2),traditional polymer microspheres have poor expandability and plugging properties.Based on previous work,a systematic evaluation of the expansion performance,dispersion rheological properties,stability,deep migration,anti-CO_(2) channeling and enhanced oil recovery ability of a novel acid-resistant polymer microsphere(DCNPM-A)was carried out under CQ oilifield conditions(salinity of85,000 mg/L,80℃,pH=3).The results show that the DCNPM-A microsphere had a better expansion performance than the traditional microsphere,with a swelling rate of 13.5.The microsphere dispersion with a concentration of 0.1%-0.5%had the advantages of low viscosity,high dispersion and good injectability in the low permeability fractured core.In the acidic environment of supercritical CO_(2),DCNPM-A microspheres showed excellent stability and could maintain strength for over 60 d with less loss.In core experiments,DCNPM-A microspheres exhibited delayed swelling characteristics and could effectively plug deep formations.With a plugging rate of 95%,the subsequent enhanced oil recovery of CO_(2) flooding could reach 21.03%.The experimental results can provide a theoretical basis for anti-CO_(2)channeling and enhanced oil recovery in low-permeability fractured reservoirs.展开更多
Rapid and timely testing is essential to minimize the COVID-19 spread. Decision makers and policy planners need to determine the equal distribution and accessibility of testing sites. This study mainly examines the sp...Rapid and timely testing is essential to minimize the COVID-19 spread. Decision makers and policy planners need to determine the equal distribution and accessibility of testing sites. This study mainly examines the spatial equality of COVID-19 testing sites that maintain a zero COVID policy in Guangzhou City. The study has identified the spatial disparities of COVID testing sites, characteristics of testing locations, and accessibility. The study has obtained information on COVID testing sites in Guangzhou City and population data. Point pattern analyses, Euclidian distance and allocation, and network analyses are the main methods used to achieve the research objectives, and 1183 total COVID testing sites can be recognized in Guangzhou City. Results revealed that spatial disparities could be noticed over the study area. Testing locations of Guangzhou City are highly clustered. The most significant testing sites are located in Haizhu District, which has the third largest population. The highest population density can be identified in Yuexiu District. However, only 94 testing sites are located there. According to all the results, higher disparities can be identified, and a lack of testing sites is located in the north part of the study area. Some people in the northern part have to travel more than 10 km to reach a testing site. Finally, this paper suggests increasing the number of testing sites in the north and south parts of the study area and keeping the same distribution, considering the area, total population, and population density. This kind of research will be helpful to decision-makers in making proper decisions to maintain a zero COVID policy.展开更多
A series of Ni/ZSM-5 containing a small amount of Ni was prepared by an ion exchanged method.The impact of the n(SiO_(2))/n(Al_(2)O_(3))ratio on the catalytic activity was studied using the samples 0.09Ni/ZSM-5(60)and...A series of Ni/ZSM-5 containing a small amount of Ni was prepared by an ion exchanged method.The impact of the n(SiO_(2))/n(Al_(2)O_(3))ratio on the catalytic activity was studied using the samples 0.09Ni/ZSM-5(60)and 0.09Ni/ZSM-5(130).To determine the interaction between the Ni species and acid sites on the surface of the catalyst,the catalysts were characterized by N2 adsorption-desorption,X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-vis spectroscopy.The performance of the catalysts for the catalytic oligomerization of 1-hexene was investigated in detail.The nickel species were found to be uniformly distributed in all the catalysts.It was discovered that the oligomerization activity of the catalyst can be improved using Ni species;however,the contribution of Brønsted acids in oligomerization reactions is greater than that of Ni sites and Lewis acids.展开更多
Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical fun...Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.展开更多
Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site...Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site density(SD)and site utilization.Herein,we reported a melamine-assisted vapor deposition approach to overcome these hindrances.The melamine not only compensates for the loss of nitrogen caused by high-temperature pyrolysis but also effectively etches the carbon substrate,increasing the external surface area and mesoporous porosity of the carbon substrate.These can provide more useful area for subsequent vapor deposition on active sites.The prepared 0.20Mela-FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine.As a result,0.20Mela-FeNC catalyst exhibits a high ORR activity with a half-wave potential(E_(1/2))of 0.861 V and 12-fold higher ORR mass activity than the FeNC in acidic media.As the cathode in a H_(2)-O_(2)PEMFCs,0.20Mela-FeNC catalyst demonstrates a high peak power density of 1.30 W cm^(-2),outstripping most of the reported Fe-N-C catalysts.The developed melamine-assisted vapor deposition approach for boosting the SD and utilization of Fe-N-C catalysts offers a new insight into high-performance ORR electrocatalysts.展开更多
Though Zn-air batteries(ZABs)are one of the most promising system for energy storage and conversion,challenge still persists in its commercial application due to the sluggish kinetics of oxygen reduction/evolution rea...Though Zn-air batteries(ZABs)are one of the most promising system for energy storage and conversion,challenge still persists in its commercial application due to the sluggish kinetics of oxygen reduction/evolution reaction(ORR/OER).Hereby,a polyvinylidene fluoride(PVDF)-assisted pyrolysis strategy is proposed to develop a novel corrugated plate-like bifunctional electrocatalyst using two-dimensional zeolitic imidazolate frameworks(2D ZIF-67)as the precursor.The employed PVDF plays an important role in inheriting the original 2D structure of ZIF-67 and modulating the composition of the final products.As a result,a corrugated plate-like electrocatalyst,high-density Co nanoparticles decorated 2D Co,N,and F tri-doped carbon nanosheets,can be obtained.The acquired electrocatalyst enables efficient active sites and rapid mass transfer simultaneously,thus showing appreciable electrocatalytic performance for rechargeable Zn-air batteries.Undoubtedly,our proposed strategy offers a new perspective to the design of advanced oxygen electrocatalysts.展开更多
Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups(e.g.,C=C and C=O)is a promising yet challenging endeavor.In our study,we developed a Pd/CeO_(...Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups(e.g.,C=C and C=O)is a promising yet challenging endeavor.In our study,we developed a Pd/CeO_(2) catalyst by enhancing the oxygen vacancy(O V)concentration in CeO_(2) through high-temperature treatment.This process led to the formation of an interface structure ideal for supporting the hydrogenation of methyl oleate to methyl stearate.Specifi cally,metal Pd^(0) atoms bonded to the O V in defective CeO_(2) formed Pd^(0)-O v-Ce^(3+)interfacial sites,enabling strong electron transfer from CeO_(2) to Pd.The interfacial sites exhibit a synergistic adsorption eff ect on the reaction substrate.Pd^(0) sites promote the adsorption and activation of C=C bonds,while O V preferably adsorbs C=O bonds,mitigating competition with C=C bonds for Pd^(0) adsorption sites.This synergy ensures rapid C=C bond activation and accelerates the attack of active H*species on the semi-hydrogenated intermediate.As a result,our Pd/CeO_(2)-500 catalyst,enriched with Pd^(0)-O v-Ce^(3+)interfacial sites,dem-onstrated excellent hydrogenation activity at just 30℃.The catalyst achieved a Cis-C18:1 conversion rate of 99.8% and a methyl stearate formation rate of 5.7 mol/(h·g metal).This work revealed the interfacial sites for enhanced hydrogenation reactions and provided ideas for designing highly active hydrogenation catalysts.展开更多
The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)...The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.展开更多
The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic ...The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.展开更多
A descriptive survey was conducted in Eastern Samar to identify the Caulerpa species, sites where these species exhibit massive populations, and the most preferred edible species. Results revealed that only four of th...A descriptive survey was conducted in Eastern Samar to identify the Caulerpa species, sites where these species exhibit massive populations, and the most preferred edible species. Results revealed that only four of the eleven species, C. racemosa, C. lentillifera, C. chemnitzia var. peltata, and C. cylindracea, have massive populations;The four Caulerpa sites are the municipalities of Arteche, Guiuan, Salcedo (Matarinao Bay) and Quinapondan, and species C. racemosa, C. lentillifera, and C. chemnitzia var. peltata are most preferred edible species which are considered in the local diet. The study concludes that the distribution of Caulerpa in Eastern Samar is area-specific and should therefore be considered in resource planning and management, particularly in relation to aquaculture.展开更多
The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ab...The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of challenge.Here,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 h.Interestingly,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such catalysts.The results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation.展开更多
An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant s...An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.展开更多
Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air bat...Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.展开更多
Designing flexible free-standing air-electrode with efficient OER/ORR performance is of vital importance for the application of Zinc-air batteries in flexible electronics.Herein,a flexible free-standing electrode(Ni/F...Designing flexible free-standing air-electrode with efficient OER/ORR performance is of vital importance for the application of Zinc-air batteries in flexible electronics.Herein,a flexible free-standing electrode(Ni/Fe-NC/NCF/CC)is synthesized by in-situ coupling of binary Ni/Fe-NC nanocubes and N-doped carbon nanofibers(NCF)rooted on carbon cloth.The highly dispersed binary Ni/Fe-NC sites ensure excellent ORR activity and create efficient OER active sites relative to Ni-NC and Fe-NC.The in-situ coupling of Ni/Fe-NC and NCF constructs a 3D interconnected network structure that not only provides abundant and stabilized reactive sites but also guarantees fast electron transfer and gas transportation,thus achieving efficient and fast operation of ORR/OER.Therefore,Ni/Fe-NC/NCF/CC displays a much positive potential(0.952 V)at 4.0 mA cm^(-2)for ORR and a low OER overpotential(310 mV)at 50 mA cm^(-2).The Zinc-air battery with Ni/Fe-NC/NCF/CC air-electrode exhibits excellent battery performance with outstanding discharge/charge durability for 2150 cycles.The flexible Zn-air batteries with foldable mechanical properties display a high power density of 105.0 mW cm^(-2).This work widened the way to prepare flexible bifunctional air-electrode by designing composition/structure and in-situ coupling.展开更多
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
The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporat...The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.展开更多
基金the Natural Science Foundation of China(11922415,12274471)Guangdong Basic and Applied Basic Research Foundation(2022A1515011168,2019A1515011718,2019A1515011337)the Key Research and Development Program of Guangdong Province,China(2019B110209003).
文摘We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in S_(v)–In_(2)S_(3)@2H–MoTe_(2).The X-ray absorption near-edge structure shows that the formation of S_(v)–In_(2)S_(3)@2H–MoTe_(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface.The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption,time-resolved,and in situ diffuse reflectance–Infrared Fourier transform spectroscopy.A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S_(v)–In_(2)S_(3)@2H–MoTe_(2)(5)photogenerated carrier concentration relative to pristine S_(v)–In_(2)S_(3).Benefiting from lower carrier transport activation energy,an internal quantum efficiency of 94.01%at 380 nm was used for photocatalytic CO_(2)RR.This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO_(2)RR.
基金supported by China Natural Science Foundation(Grant No.52274053)Beijing Natural Science Foundation(Grant No.3232028)Open Fund of State Key Laboratory of Offshore Oil Exploitation(Grant No.CCL2021RCPS0515KQN)。
文摘Spontaneous imbibition(SI)is an important mechanism for enhancing oil recovery in low-permeability reservoirs.Due to the strong heterogeneity,and the non-Darcy flow,the construction of SI model for lowpermeability reservoirs is extremely challenging.Commonly,traditional SI models based on single or averaged capillary tortuosity ignore the influence of heterogeneity of pore seepage channels and the threshold pressure(TP)on imbibition.Therefore,in this work,based on capillary model and fractal theory,a mathematical model of characterizing SI considering heterogeneity of pore seepage channels is established.On this basis,the threshold pressure was introduced to determine the pore radius at which the wetted phase can displace oil.The proposed new SI model was verified by imbibition experimental data.The study shows that for weakly heterogeneous cores with permeability of 0-1 m D,the traditional SI model can characterize the imbibition process relatively accurately,and the new imbibition model can increase the coefficient of determination by 1.05 times.However,traditional model has serious deviations in predicting the imbibition recovery for cores with permeability of 10-50 m D.The new SI model coupling with heterogeneity of pore seepage channels and threshold pressure effectively solves this problem,and the determination coefficient is increased from 0.344 to 0.922,which is increased by2.68 times.For low-permeability reservoirs,the production of the oil in transitional pores(0.01-0.1μm)and mesopores(0.1-1μm)significantly affects the imbibition recovery,as the research shows that when the heterogeneity of pore seepage channels is ignored,the oil recovery in transitional pores and mesopores decreases by 7.54%and 4.26%,respectively.Sensitivity analysis shows that increasing interfacial tension,decreasing contact angle,oil-water viscosity ratio and threshold pressure will increase imbibition recovery.In addition,there are critical values for the influence of these factors on the imbibition recovery,which provides theoretical support for surfactant optimization.
基金supported by the Innovation Foundation of Graduate Student of Harbin Normal University (No.HSDBSCX2023-3),China。
文摘Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes(ZMAs)severely restrict their applications.To address these issues,we design the asymmetric Zn-N_(4) atomic sites embedded hollow fibers(AS-IHF)as the flexible host for stable ZMAs.Through introducing different nitrogen resources in the synthesis,two kinds of coordination,i,e.Zn-N(pyridinic)and Zn-N(pyrrolic),are introduced in the Zn-N_(4) atomic module synchronously.The asymmetric Zn-N_(4) module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption.Meanwhile,the highly porous structure of the hollow fiber effectively reduces local current density,homogenize Zn ion flux,and alleviate structure stress.All the advantages endow the high efficiency and good stability for Zn plating/stripping.Both theoretical and experimental results demonstrate the high reversibility,low nucleation overpotential,and dendritefree behavior of the AS-IHF@Zn anode,which afford the high stability in high-rate and long-term cycling.Moreover,the solid-state Zn-ion hybrid capacitor(ZIHC)based on AS-IHF@Zn anode shows the high flexibility,reliability,and superior long-term cycling capability in a wide-range of temperatures(-20-25℃).Therefore,the present work not only gives a new strategy for modulating local environments of single atomic sites,but also propels the development of flexible power sources for diverse electronics.
基金supported by the Fund of State Key Laboratory of Deep Oil and Gas,China University of Petroleum (East China) (SKLDOG2024-ZYRC-06)Key Program of National Natural Science Foundation of China (52130401)+2 种基金National Natural Science Foundation of China (52104055,52250410349)Major Science and Technology Project of China National Petroleum Corporation Limited (2021ZZ01-08)Shandong Provincial Natural Science Foundation,China (ZR2021ME171)。
文摘CO_(2) flooding is a vital development method for enhanced oil recovery in low-permeability reservoirs,However,micro-fractures are developed in low-permeability reservoirs,which are essential oil flow channels but can also cause severe CO_(2) gas channeling problems.Therefore,anti-gas channeling is a necessary measure to improve the effect of CO_(2) flooding.The kind of anti-gas channeling refers to the plugging of fractures in the deep formation to prevent CO_(2) gas channeling,which is different from the wellbore leakage.Polymer microspheres have the characteristics of controllable deep plugging,which can achieve the profile control of low-permeability fractured reservoirs.In acidic environments with supercritical CO_(2),traditional polymer microspheres have poor expandability and plugging properties.Based on previous work,a systematic evaluation of the expansion performance,dispersion rheological properties,stability,deep migration,anti-CO_(2) channeling and enhanced oil recovery ability of a novel acid-resistant polymer microsphere(DCNPM-A)was carried out under CQ oilifield conditions(salinity of85,000 mg/L,80℃,pH=3).The results show that the DCNPM-A microsphere had a better expansion performance than the traditional microsphere,with a swelling rate of 13.5.The microsphere dispersion with a concentration of 0.1%-0.5%had the advantages of low viscosity,high dispersion and good injectability in the low permeability fractured core.In the acidic environment of supercritical CO_(2),DCNPM-A microspheres showed excellent stability and could maintain strength for over 60 d with less loss.In core experiments,DCNPM-A microspheres exhibited delayed swelling characteristics and could effectively plug deep formations.With a plugging rate of 95%,the subsequent enhanced oil recovery of CO_(2) flooding could reach 21.03%.The experimental results can provide a theoretical basis for anti-CO_(2)channeling and enhanced oil recovery in low-permeability fractured reservoirs.
文摘Rapid and timely testing is essential to minimize the COVID-19 spread. Decision makers and policy planners need to determine the equal distribution and accessibility of testing sites. This study mainly examines the spatial equality of COVID-19 testing sites that maintain a zero COVID policy in Guangzhou City. The study has identified the spatial disparities of COVID testing sites, characteristics of testing locations, and accessibility. The study has obtained information on COVID testing sites in Guangzhou City and population data. Point pattern analyses, Euclidian distance and allocation, and network analyses are the main methods used to achieve the research objectives, and 1183 total COVID testing sites can be recognized in Guangzhou City. Results revealed that spatial disparities could be noticed over the study area. Testing locations of Guangzhou City are highly clustered. The most significant testing sites are located in Haizhu District, which has the third largest population. The highest population density can be identified in Yuexiu District. However, only 94 testing sites are located there. According to all the results, higher disparities can be identified, and a lack of testing sites is located in the north part of the study area. Some people in the northern part have to travel more than 10 km to reach a testing site. Finally, this paper suggests increasing the number of testing sites in the north and south parts of the study area and keeping the same distribution, considering the area, total population, and population density. This kind of research will be helpful to decision-makers in making proper decisions to maintain a zero COVID policy.
基金Financial support was obtained from the State Key Laboratory of Petroleum Molecular&Process Engineering(24-ZC0607-0099)the Natural Science Foundation of China(21706177 and 22378293).
文摘A series of Ni/ZSM-5 containing a small amount of Ni was prepared by an ion exchanged method.The impact of the n(SiO_(2))/n(Al_(2)O_(3))ratio on the catalytic activity was studied using the samples 0.09Ni/ZSM-5(60)and 0.09Ni/ZSM-5(130).To determine the interaction between the Ni species and acid sites on the surface of the catalyst,the catalysts were characterized by N2 adsorption-desorption,X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-vis spectroscopy.The performance of the catalysts for the catalytic oligomerization of 1-hexene was investigated in detail.The nickel species were found to be uniformly distributed in all the catalysts.It was discovered that the oligomerization activity of the catalyst can be improved using Ni species;however,the contribution of Brønsted acids in oligomerization reactions is greater than that of Ni sites and Lewis acids.
基金the following funding agencies for supporting this work: the National Natural Science Foundation of China (22025502, U23A20552, 22379026, 22222901, 22175022)the Natural Science Foundation of Shanghai (23ZR1407000)the Science and Technology Commission of Shanghai Municipality (21DZ1206800)
文摘Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.
基金granted by the National Natural Science Foundation of China(22172134,22288102)the National Key Research and Development Program of China(2017YFA0206500)
文摘Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site density(SD)and site utilization.Herein,we reported a melamine-assisted vapor deposition approach to overcome these hindrances.The melamine not only compensates for the loss of nitrogen caused by high-temperature pyrolysis but also effectively etches the carbon substrate,increasing the external surface area and mesoporous porosity of the carbon substrate.These can provide more useful area for subsequent vapor deposition on active sites.The prepared 0.20Mela-FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine.As a result,0.20Mela-FeNC catalyst exhibits a high ORR activity with a half-wave potential(E_(1/2))of 0.861 V and 12-fold higher ORR mass activity than the FeNC in acidic media.As the cathode in a H_(2)-O_(2)PEMFCs,0.20Mela-FeNC catalyst demonstrates a high peak power density of 1.30 W cm^(-2),outstripping most of the reported Fe-N-C catalysts.The developed melamine-assisted vapor deposition approach for boosting the SD and utilization of Fe-N-C catalysts offers a new insight into high-performance ORR electrocatalysts.
基金supported by the National Natural Science Foundation of China (No.21908049,52274298,and 51974114)Hunan Provincial Natural Science Foundation of China (No.2022JJ40035,2020JJ4175,2024JJ4022,2023JJ30277)+2 种基金Science and Technology Talents Lifting Project of Hunan Province (No.2022TJ-N16)Open Fund of State Key Laboratory of Advanced Metallurgy,University of Science and Technology Beijing (K1:24-09)Postdoctoral Fellowship Program (No.GZC20233205)。
文摘Though Zn-air batteries(ZABs)are one of the most promising system for energy storage and conversion,challenge still persists in its commercial application due to the sluggish kinetics of oxygen reduction/evolution reaction(ORR/OER).Hereby,a polyvinylidene fluoride(PVDF)-assisted pyrolysis strategy is proposed to develop a novel corrugated plate-like bifunctional electrocatalyst using two-dimensional zeolitic imidazolate frameworks(2D ZIF-67)as the precursor.The employed PVDF plays an important role in inheriting the original 2D structure of ZIF-67 and modulating the composition of the final products.As a result,a corrugated plate-like electrocatalyst,high-density Co nanoparticles decorated 2D Co,N,and F tri-doped carbon nanosheets,can be obtained.The acquired electrocatalyst enables efficient active sites and rapid mass transfer simultaneously,thus showing appreciable electrocatalytic performance for rechargeable Zn-air batteries.Undoubtedly,our proposed strategy offers a new perspective to the design of advanced oxygen electrocatalysts.
基金This work was supported by the National Key Research and Development Program of China(No.2023YFB4203800).
文摘Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups(e.g.,C=C and C=O)is a promising yet challenging endeavor.In our study,we developed a Pd/CeO_(2) catalyst by enhancing the oxygen vacancy(O V)concentration in CeO_(2) through high-temperature treatment.This process led to the formation of an interface structure ideal for supporting the hydrogenation of methyl oleate to methyl stearate.Specifi cally,metal Pd^(0) atoms bonded to the O V in defective CeO_(2) formed Pd^(0)-O v-Ce^(3+)interfacial sites,enabling strong electron transfer from CeO_(2) to Pd.The interfacial sites exhibit a synergistic adsorption eff ect on the reaction substrate.Pd^(0) sites promote the adsorption and activation of C=C bonds,while O V preferably adsorbs C=O bonds,mitigating competition with C=C bonds for Pd^(0) adsorption sites.This synergy ensures rapid C=C bond activation and accelerates the attack of active H*species on the semi-hydrogenated intermediate.As a result,our Pd/CeO_(2)-500 catalyst,enriched with Pd^(0)-O v-Ce^(3+)interfacial sites,dem-onstrated excellent hydrogenation activity at just 30℃.The catalyst achieved a Cis-C18:1 conversion rate of 99.8% and a methyl stearate formation rate of 5.7 mol/(h·g metal).This work revealed the interfacial sites for enhanced hydrogenation reactions and provided ideas for designing highly active hydrogenation catalysts.
基金supported by the National Natural Science Foundation of China(22221005 and 22008033).
文摘The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.
基金supported by the National Natural Science Foundation of China(22109100,22075203)Guangdong Basic and Applied Basic Research Foundation(2022A1515011677)+1 种基金Shenzhen Science and Technology Project Program(JCYJ2021032409420401)Natural Science Foundation of SZU(000002111605).
文摘The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.
文摘A descriptive survey was conducted in Eastern Samar to identify the Caulerpa species, sites where these species exhibit massive populations, and the most preferred edible species. Results revealed that only four of the eleven species, C. racemosa, C. lentillifera, C. chemnitzia var. peltata, and C. cylindracea, have massive populations;The four Caulerpa sites are the municipalities of Arteche, Guiuan, Salcedo (Matarinao Bay) and Quinapondan, and species C. racemosa, C. lentillifera, and C. chemnitzia var. peltata are most preferred edible species which are considered in the local diet. The study concludes that the distribution of Caulerpa in Eastern Samar is area-specific and should therefore be considered in resource planning and management, particularly in relation to aquaculture.
基金financially supported by the National Natural Science Foundation of China with grant number of 22172082 and 21978137。
文摘The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of challenge.Here,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 h.Interestingly,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such catalysts.The results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation.
基金funded by the Science and Technology Project of Southwest United Graduate School of Yunnan Province(No.202302AQ370002)the National Natural Science Foundation of China(No.22206066)。
文摘An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.
基金financially supported by the National Key R&D Program of China(2022YFB4004100)the National Natural Science Foundation of China(22272161)+6 种基金the Jilin Province Science and Technology Development Program(20230101367JC)financially supported by the National Natural Science Foundation of China(22073094)the Science and Technology Development Program of Jilin Province(20210402059GH)the Science and Technology Plan Projects of Yunnan Province(202101BC070001–007)the Major Science and Technology Projects for Independent Innovation of China FAW Group Co.,Ltd(20220301018GX)the essential support of the Network and Computing Center,CIAC,CASthe Computing Center of Jilin Province。
文摘Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.
基金supported by the National Natural Science Foundation of China(Grants:51861135315,U1766216,51774148,51804128,52177215,51977097)
文摘Designing flexible free-standing air-electrode with efficient OER/ORR performance is of vital importance for the application of Zinc-air batteries in flexible electronics.Herein,a flexible free-standing electrode(Ni/Fe-NC/NCF/CC)is synthesized by in-situ coupling of binary Ni/Fe-NC nanocubes and N-doped carbon nanofibers(NCF)rooted on carbon cloth.The highly dispersed binary Ni/Fe-NC sites ensure excellent ORR activity and create efficient OER active sites relative to Ni-NC and Fe-NC.The in-situ coupling of Ni/Fe-NC and NCF constructs a 3D interconnected network structure that not only provides abundant and stabilized reactive sites but also guarantees fast electron transfer and gas transportation,thus achieving efficient and fast operation of ORR/OER.Therefore,Ni/Fe-NC/NCF/CC displays a much positive potential(0.952 V)at 4.0 mA cm^(-2)for ORR and a low OER overpotential(310 mV)at 50 mA cm^(-2).The Zinc-air battery with Ni/Fe-NC/NCF/CC air-electrode exhibits excellent battery performance with outstanding discharge/charge durability for 2150 cycles.The flexible Zn-air batteries with foldable mechanical properties display a high power density of 105.0 mW cm^(-2).This work widened the way to prepare flexible bifunctional air-electrode by designing composition/structure and in-situ coupling.
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 of the Doctoral Research Initiation Foundation of Linyi University(LYDX2020BS016)the National Natural Science Foundation of Shandong Province(ZR2021QB208,ZR2022MB054)+4 种基金the National Natural Science Foundation of China(22305262)SIAT Innovation Program for Excellent Young Researchers(2022)Shenzhen Science and Technology Program Grant(RCJC20200714114435061,ZDSYS20220527171406014)the City University of Hong Kong Donation Research Grants(9220061 and 9229021)City University of Hong Kong Strategic Research Grant(SRG 7005505)。
文摘The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.