Organic-rich mudstones and shales,which hold significant potential for shale oil resources,characterize the first member of the Upper Cretaceous Qingshankou Formation(K_(2)qn~1)in the Sanzhao sag of the Songliao Basin...Organic-rich mudstones and shales,which hold significant potential for shale oil resources,characterize the first member of the Upper Cretaceous Qingshankou Formation(K_(2)qn~1)in the Sanzhao sag of the Songliao Basin,NE China.Focusing on 30 core samples obtained from the first shale oil parameter well,named SYY3 in the study area,we systematically analyzed the composition and stratigraphic distribution of the K_(2)qn~1 heteroatomic compounds using electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry(ESI FT-ICR MS),to assess their geological relevance to shale oil.The findings indicate that in the negative ion mode,the heteroatomic compounds predominantly consist of N_(1),N_(1)O_(1)-N_(1)O_(8),O_(1)-O_(8),O_(1)S_(1)-O_(6)S_(1);contrastingly,in the positive ion mode,they are primarily composed of N_(1)-N_(2),N_(1)O_(1)-N_(1)O_(4),N_(2)O_(1),O_(1)-O_(4),O_(1)S_(1)-O_(2)S_(1).Heteroatomic compound distributions vary significantly with depth in the negative ion mode,with minor variations in the positive ion mode.These distributions are categorized into three types based on the negative ion ratio((N_(1)+N_(1)O_(x))/O_(x)):TypeⅠ(>1.5),TypeⅡ(0.8-1.5),and TypeⅢ(<0.8);typesⅠandⅡgenerally exhibit a broader range of carbon numbers compared to TypeⅢ.The distribution of double bond equivalent(DBE)values across various sample types exhibits minimal variance,whereas that of carbon numbers shows substantial differences.Variations in heteroatomic compound compositions among the samples might have resulted from vertical sedimentary heterogeneity and differing biotic contributions.TypeⅢsamples show a decrease in total organic carbon(TOC)and free oil content(S_(1))compared to typesⅠandⅡ,but an increased oil saturation index(OSI),indicating a lower content of free oil but a higher proportion of movable oil.The reduced content of N-containing compounds implies lower paleolake productivity during deposition,leading to a reduction in TOC and S_(1).A lower TOC can enhance oil movability due to reduced oil adsorption,and the decreased presence of polar nitrogenous macromolecules with fewer highC-number heteroatomic compounds further promote shale oil movability.Additionally,the negative ion ratios of N1/N1O1and O2/O1 exhibit positive and negative correlations with the values of TOC,S_(1),and extractable organic matter(EOM),respectively,indicating that the salinity and redox conditions of the depositional water body are the primary controlling factors for both organic matter enrichment and shale oil accumulation.展开更多
Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limi...Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limit its PEC activity for water reduction.Here,we developed a heterostructure photocathode consisting of the Cu-doped NiO(Cu:NiO)hole selective layer(HSL)and Ni-doped CuFeO_(2)(Ni:CuFeO_(2))active layer by simply annealing a homogeneous Cu-Fe oxalate layer grown on the Ni film deposited on the fluorine doped tin oxide(FTO)substrate.The obtained heterostructure of Cu:NiO/Ni:CuFeO_(2) with enhanced charge carrier transportability and high-quality interface greatly promotes the separation of photogenerated carriers.Accordingly,the Cu:NiO/Ni:CuFeO_(2) photocathode exhibits a high photocurrent density of~0.9 mA·cm^(-2 )at 0.2 V(vs.reversible hydrogen electrode,RHE),outperforming most of the reported bare CuFeO_(2) photocathodes in the literature.And the photocurrent density can be further improved to 1.2 mA·cm^(-2) after decorating NiSx cocatalyst.展开更多
Solid-waste-based activated carbon(AC)was utilized as a carbon source to synthesize a series of carbon-based functional material RAC-X(X=P and S,where P and S denote phosphoric and sulfuric acids,respectively).The tol...Solid-waste-based activated carbon(AC)was utilized as a carbon source to synthesize a series of carbon-based functional material RAC-X(X=P and S,where P and S denote phosphoric and sulfuric acids,respectively).The toluene adsorption capacities of the regeneration AC(RAC)samples can be significantly improved by adopting the heteroatomic modification strategy.RAC-P and RAC-S have the same specific surface area(1156 m^(2)/g)and similar porous structures.However,they have different toluene adsorption capacities,with 316.22 mg/g for RAC-P and 460.12 mg/g for RAC-S,which are 1.6 and 2.4 times greater than that for RAC.The X-ray photoelectron spectroscopy measurements showed that the increase in the amount ofπ–π^(2)chemical bond over the AC surface results in the improvement of the toluene adsorption performance.The density functional theory results showed that the S-containing functional groups loaded near the defect sites of RAC-S promote toluene adsorption.Moreover,reusability tests showed that RAC-S still retains 86%of its adsorption activity after four consecutive adsorption–desorption experiments.This indicates that the heteroatomic modification method affords excellent toluene adsorption performance and recycling practicability,which not only is beneficial for achieving the rational utilization of solid waste resources but also provides a practical method for the efficient elimination of volatile organic compounds.展开更多
Although Fe-Ni combination performs well in transition metal-based oxygen evolution reaction(OER)electrocatalysts,there are lack of clear and general regulations mechanism to fully play the synergistic catalytic effec...Although Fe-Ni combination performs well in transition metal-based oxygen evolution reaction(OER)electrocatalysts,there are lack of clear and general regulations mechanism to fully play the synergistic catalytic effect.Here,we made the utmost of the interaction of Fe–Ni heteroatomic pair to obtain a highly active Fe-Ni(oxy)hydroxide catalytic layer on iron foam(IF)and nickel foam(NF)by in-situ electrochemical deposition and rapid surface reconstruction,which only required 327 and 351 mV overpotential to provide a large current of 1,000 mA·cm^(−2),respectively.The results confirm that the moderate Ni-rich heteroatomic bonding(Ni–O–Fe–O–Ni)formed by adjusting the Ni/Fe ratio on the catalyst surface is important to offer predominant OER performance.Fe is a key component that enhances OER activity of Ni(O)OH,but Fe-rich structural surface formed by Fe–O–Ni–O–Fe bonding is not ideal.Finally,the remarkable oxygen evolution performance of the prepared Ni2Fe(O)OH/IF and FeNi2(O)OH/NF can be chalked up to the optimized electronic structure of Fe–Ni heteroatomic bonding,the efficient gas spillover,the fast electron transport,and nanosheet clusters morphology.In summary,our work suggests a comprehensive regulation mechanism for the construction of efficient Fe-Ni(oxy)hydroxide catalytic layer on inexpensive,stable,and self-supporting metallic material surface.展开更多
As a potential adsorption material,it is still a challenge for activated carbon fiber(ACF)in efficient adsorption of ethanol due to its nonpolar surface,which is mainly emitted from the grain drying industry.This stud...As a potential adsorption material,it is still a challenge for activated carbon fiber(ACF)in efficient adsorption of ethanol due to its nonpolar surface,which is mainly emitted from the grain drying industry.This study prepared surface polarity-modified ACF using the heteroatom doping method.The modified ACF possessed a richer array of strongly polar oxygen/nitrogen-containing functional groups(primarily phenolic hydroxyl and lactone groups),a larger specific surface are1,and a more developed micropore structure.The adsorption capacities of ethanol for O-ACF and N-ACF were 4.110 mmol/g and 1.698 mmol/g,respectively,which were 11.3 times and 4.7 times those of unmodified ACF.This was a significant improvement over our previous work(0.363 mmol/g).The improvement of adsorption capacity for the N-ACF was mainly due to the higher specific surface are1,greater number of micropores(more adsorption sites)and abundant existence of defects,whereas,for O-ACF,the improvement mainly relied on the abundant presence of oxygen-containing functional groups on the surface.However,water had a negative effect on the adsorption of ethanol for the modified ACF due to competitive adsorption and the disappearance of capillary condensation.It was further revealed that the adsorption process of ethanol and water was quite different.It obeyed the linear driving force(LDF)model for ethanol adsorption,however,the intraparticle diffusion(IPD)model for water adsorption.展开更多
Electrocatalyst activity and stability demonstrate a“seesaw”relationship.Introducing vacancies(Vo)enhances the activity by improving reactant affinity and increasing accessible active sites.However,deficient or exce...Electrocatalyst activity and stability demonstrate a“seesaw”relationship.Introducing vacancies(Vo)enhances the activity by improving reactant affinity and increasing accessible active sites.However,deficient or excessive Vo reduces polysulfide adsorption and lowers catalytic stability.Herein,a novel“heteroatoms synergistic anchoring vacancies”strategy is proposed to address the trade-off between high activity and stability.Phosphorus-doped CoSe_(2)with remained rich selenium vacancies(P-CS-Vo-0.5)was synthesized by producing abundant selenium Vo followed by controlled P atom doping.Atomic-scale microstructure analysis elucidated a dynamic process of surface vacancy generation and the subsequent partial occupation of these vacancies by P atoms.Density functional theory simulations and in situ Raman tests revealed that the Se vacancies provide highly active catalytic sites,accelerating polysulfide conversion,while P incorporation effectively reduces the surface energy of Se vacancies and suppresses their inward migration,enhancing structural robustness.The battery with the optimal P-CS-Vo-0.5 separator delivers an initial discharge capacity of 1306.7 mAh g^(-1)at 0.2C,and maintain 5.04 mAh cm^(-2)at a high sulfur loading(5.7 mg cm^(-2),5.0μL mg^(-1)),achieving 95.1%capacity retention after 80 cycles.This strategy of modifying local atomic environments offers a new route to designing highly active and stable catalysts.展开更多
Nickel-rich(Ni≥90%)layered oxides materials have emerged as a promising candidate for nextgeneration high-energy-density lithium-ion batteries(LIBs).However,their widespread application is hindered by structural fati...Nickel-rich(Ni≥90%)layered oxides materials have emerged as a promising candidate for nextgeneration high-energy-density lithium-ion batteries(LIBs).However,their widespread application is hindered by structural fatigue and lattice oxygen loss.In this work,an epitaxial surface rock-salt nanolayer is successfully developed on the LiNi_(0.9)Co_(0.1)O_(2)sub-surface via heteroatom anchoring utilizing high-valence element molybdenum modification.This in-situ formed conformal buffer phase with a thickness of 1.2 nm effectively suppresses the continuous interphase side-reactions,and thus maintains the excellent structure integrity at high voltage.Furthermore,theoretical calculations indicate that the lattice oxygen reversibility in the anion framework of the optimized sample is obviously enhanced due to the higher content of O 2p states near the Fermi level than that of the pristine one.Meanwhile,the stronger Mo-O bond further reduces cell volume alteration,which improves the bulk structure stability of modified materials.Besides,the detailed charge compensation mechanism suggests that the average oxidation state of Ni is reduced,which induces more active Li+participating in the redox reactions,boosting the cell energy density.As a result,the uniquely designed cathode materials exhibit an extraordinary discharge capacity of 245.4 mAh g^(-1)at 0.1 C,remarkable rate performance of 169.3 mAh g^(-1)at 10 C at 4.5 V,and a high capacity retention of 70.5% after 1000 cycles in full cells at a high cut-off voltage of 4.4 V.This strategy provides an valuable insight into constructing distinctive heterostructure on highperformance Ni-rich layered cathodes for LIBs.展开更多
The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally...The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.展开更多
Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incor...Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe(oxy)hydroxide(Mn-NiFeOOH/LDH)heterojunction.Mn doping regulates heterojunction morphology(reducing nanoparticles and becoming thinner and denser nanosheets),Ni/Fe ratio and valence states(Ni^(2+),Ni^(3+),and Ni^(3+Δ))of Ni ions.The former could effectively increase surface active sites,and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction,en-abling more Ni^(2+)convert to Ni^(3+/3+Δ)that have higher intrinsic OER activity.As a result,the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm^(-2) and 296 mV@500 mA cm^(-2),and the improved OER performance are outdo to those of commercial RuO_(2) catalyst for OER.Moreover,the Mn-NiFeOOH/LDH affords the earliest initial potential(1.392 V vs.RHE),corresponds to a recorded low overpotential(162 mV).Based on the density functional theory(DFT),Mn dopants can alter intermedi-ate adsorption energy and effectively decrease∗OOH’s energy barrier.This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.展开更多
Heavy oil,constituting a significant portion of global oil reserves,presents unique challenges in extraction and processing due to its high viscosity,largely influenced by asphaltenes and their heteroatom content.This...Heavy oil,constituting a significant portion of global oil reserves,presents unique challenges in extraction and processing due to its high viscosity,largely influenced by asphaltenes and their heteroatom content.This study employs molecular dynamics(MD)simulations to investigate the selfaggregation and adsorption mechanisms of heteroatom/non-heteroatom asphaltenes,comparing linear and island structural configurations.Key findings reveal that linear heteroatom asphaltenes form dense,multi-layered aggregates,while island heteroatom asphaltenes exhibit stronger aggregation energy.On solid surfaces,linear asphaltenes display multi-layered adsorption,whereas island asphaltenes adopt a dispersed structure with higher adsorption energy,making them more resistant to removal.Compared to non-heteroatom asphaltenes,heteroatom asphaltenes significantly enhance the aggregation energy of the asphaltene itself and the interaction energy with light oil components,reducing the diffusion capacity of oil droplets and increasing viscosity.Although the viscosity of island heteroatom asphaltene oil drops is the largest,the role of heteroatom in linear asphaltene is more obvious,and linear heteroatom asphaltene and non-heteroatom show great differences in properties.Additionally,heteroatom-containing oil droplets exhibit stronger interactions with solid surfaces,driven by the influence of heteroatom asphaltenes on lighter oil components.These insights provide a deeper understanding of heavy oil viscosity mechanisms,offering a foundation for developing targeted viscosity-reduction strategies and optimizing heavy oil recovery and processing techniques.展开更多
Zinc-ion hybrid capacitors (ZIHCs) have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental friendliness.However,their progress has been hampered by low energy...Zinc-ion hybrid capacitors (ZIHCs) have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental friendliness.However,their progress has been hampered by low energy and power density,as well as unsatisfactory long-cycle stability,mainly due to the lack of suitable electrode materials.In this context,we have developed manganese single atoms implanted in nitrogen-doped porous carbon nanosheets (MnSAs/NCNs) using a metal salt template method as cathodes for ZIHCs.The metal salt serves a dual purpose in the synthesis process:It facilitates the uniform dispersion of Mn atoms within the carbon matrix and acts as an activating agent to create the porous structure.When applied in ZIHCs,the MnSAs/NCNs electrode demonstrates exceptional performance,including a high capacity of 203 m Ah g^(-1),an energy density of 138 Wh kg^(-1)at 68 W kg^(-1),and excellent cycle stability with 91%retention over 10,000 cycles.Theoretical calculations indicate that the introduced Mn atoms modulate the local charge distribution of carbon materials,thereby improving the electrochemical property.This work demonstrates the significant potential of carbon materials with metal atoms in zinc-ion hybrid capacitors,not only in enhancing electrochemical performance but also in providing new insights and methods for developing high-performance energy storage devices.展开更多
Heterocyclic compounds play an important role in organic hole transport materials(HTMs)for perovskite solar cells(PSCs).Herein,a series of linear D-π-D HTMs(O-CBz,S-CBz,SO_(2)-CBz)with different dibenzoheterocycles c...Heterocyclic compounds play an important role in organic hole transport materials(HTMs)for perovskite solar cells(PSCs).Herein,a series of linear D-π-D HTMs(O-CBz,S-CBz,SO_(2)-CBz)with different dibenzoheterocycles core(dibenzofuran,dibenzothiophene,dibenzothiophene sulfone)were designed and synthesized,and their applications in PSCs were investigated.The intrinsic properties(CV,UV-vis,hole mobility and conductivity)were systematically investigated,demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs.Benefiting from the excellent hole mobility and conductivity,good film forming ability,and outstanding charge extraction and transport capability of S-CBz,FAPbI_(3)-based PSCs using S-CBz as HTM achieved a PCE of 25.0%,which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions(23.9%).Furthermore,due to the interaction between S and Pb^(2+),SCBz-based PSC devices exhibited improved stability.This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.展开更多
Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru...Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-Co O/CP with doping strategy and heterostructure was synthesized for overall water splitting.The Ru/V-Co O exhibits excellent activity for HER and OER with low overpotentials of 49, 147 m V at a current density of 10 m A/cm^(2) in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 m A/cm^(2)current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial Ru O_(2)||Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts,providing new ideas for the design and development of efficient and stable electrocatalysts.展开更多
Designing exceptional-performance and long-lasting oxygen reduction reaction(ORR)catalysts is a critical challenge for the development of rechargeable Zn-air batteries(ZABs).In this study,we introduce a metal-free ORR...Designing exceptional-performance and long-lasting oxygen reduction reaction(ORR)catalysts is a critical challenge for the development of rechargeable Zn-air batteries(ZABs).In this study,we introduce a metal-free ORR catalyst composed of F-N co-doped hollow carbon(FNC),specifically engineered to address the limitations of conventional catalysts.The FNC catalysts were synthesized using a template-assisted pyrolysis method,resulting in a hollow,porous architecture with a high specific surface area and numerous active sites.Concurrently,F doping optimized the electronic configuration of pyridinic nitrogen.The introduction of C-F bonds reduced the reaction energy barrier,and the resulting N-C-F configuration enhanced the stability of the nitrogen center.The catalyst exhibits outstanding ORR activity in alkaline media,exhibiting a half-wave potential(E_(1/2))of 0.87 V,surpassing that of commercial Pt/C(E_(1/2)=0.85 V).When applied to both aqueous and flexible ZAB configurations,the FNC catalyst achieved peak power densities of 172 and 85 mW cm^(-2),respectively,along with exceptional cycling stabilities exceeding 5300 and 302 h,respectively.This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs,particularly for use in flexible and wearable microelectronic devices.展开更多
The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a ...The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.展开更多
The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalyst...The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalysts by Fe^(3+)etching during the hydrothermal and chemical deposition process.The as-prepared CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4 catalyst exhibits a lowoverpotential of 225 mV at 10 mA·cm^(-2)with a Tafel slope of 30.47 mV·dec^(-1).An overall water splitting electrolyzer(CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4‖Pt/C)is constructed,delivering a voltage of 1.48 V at a current density of10 mA·cm^(-2)with excellent durability.The dynamic phase evolution during the OER process is revealed by in situ Raman and XPS measurement,which represents that the introduced V and Fe ions facilitate the formation of active CoOOH as well as modify the electronic structure of the catalyst.Density functional theory(DFT)calculations further evidence that V and Fe introduction optimize the adsorption energies of oxygen intermediates*OH and*O,respectively,thereby enabling a synergistic optimization of the multi-step OER process and advancing electrocatalytic performance.展开更多
The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(EC...The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(ECR)frequently encounter high energy barriers and competitive hydrogen evolution reactions(HERs),which are urgent problems that need to be addressed.In this study,a catalyst(P100-Fe-N/C)with homogeneous P-tuned FeN_(2)binuclear sites(N_(2)PFe-FePN_(2))was successfully synthesised,demonstrating satisfactory performance in the ECR to CO.P100-Fe-N/C attains a peak FECOof 98.01%and a normalized TOF of 664.7 h-1at-0.7 VRHE,surpassing the performance of the Fe binuclear catalyst without P and singleatoms catalysts.In the MEA cell,a FECOexceeding 90%can still be achieved.Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system's energy.The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level,which facilitates the interaction of the catalyst with CO_(2),allowing more electrons to be injected into the CO_(2)molecule at the Fe binuclear sites and inhibiting the HER.The P-tuned FeN_(2)binuclear sites effectively lower the^(*)CO desorption barrier.展开更多
Heteroatom doping is a promising strategy for designing cost-effective and stable electrocatalysts toward the oxygen evolution reaction(OER),but the enhancement mechanism remains unclear.Herein,atomic Ir-O-Cu and Ir-O...Heteroatom doping is a promising strategy for designing cost-effective and stable electrocatalysts toward the oxygen evolution reaction(OER),but the enhancement mechanism remains unclear.Herein,atomic Ir-O-Cu and Ir-O-Ir motifs are engineered into CuO nanowires via cation exchange and dehydration to elucidate the OER mechanism.Systematic characterizations confirm the atomic dispersion of Ir within the CuO lattice and the electron transfer from Ir to CuO while preserving the host structure.The asprepared single-atom Ir-doped CuO(IrSA-CuO),featuring predominant Cu-O-Ir motifs and coexisting IrO-Ir motifs,achieves a low OER overpotential of 204 mV at 10 mA cm^(-2)in 1 M KOH,coupled with a 69-fold higher mass activity than commercial IrO_(2).Furthermore,the Ir_(SA)-CuO maintains long-term stability for 300 h at 200 mA cm^(-2)with minimal overpotential alteration and an additional 120 h at500 mA cm^(-2)with overpotential increased by 15 mV.In situ Raman spectroscopy reveals that the Ir-O-Ir motifs suppress Cu^(Ⅱ) oxidation to Cu^(Ⅲ) by delaying the onset potential,enhancing the structural stability during OER.Density functional theory calculations demonstrate the Cu-O-Ir motifs lower the adsorption energy of bridged ^(*)O via asymmetric bonding,accelerating ^(*)OOH formation in the ratedetermining step.This work presents a heteroatom engineering strategy to balance electrocatalytic activity and durability,providing a blueprint for industrial electrocatalyst design.展开更多
The development of single atom catalysts(SACs)with asymmetric active sites by defect regulation provides an encourage potential for oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER),but highly challen...The development of single atom catalysts(SACs)with asymmetric active sites by defect regulation provides an encourage potential for oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER),but highly challenging.Herein,N-doped carbon(N-C)anchored atomically dispersed Ni-N_(3)site with proximity defects(Ni-N_(3)D)induced by Te atoms doping is reported.Benefitting from the inductive effect of proximity defect,the Ni-N_(3)D/Te-N-C catalyst performs excellent ORR and HER performance in alkaline and acid condition.Both in situ characterization and theoretical calculation reveal that the existence of proximity defect effect is conducive to lower rate-determining-step energy barrier of ORR and HER,thus accelerating the multielectron reaction kinetics.This work paves a novel strategy for constructing highactivity bifunctional SACs by defect engineering for development of sustainable energy.展开更多
It is a big challenge to tune the structure and composition of carbon-based anode materials to increase the active sites by a green synthesis strategy for potassium ion batteries(PIBs).Herein,the N/F/S co-doped three-...It is a big challenge to tune the structure and composition of carbon-based anode materials to increase the active sites by a green synthesis strategy for potassium ion batteries(PIBs).Herein,the N/F/S co-doped three-dimensional(3D)interconnected carbon nanosheets(NFS-CNSs)were synthesized from coal tar pitch(CTP)through a green and low-temperature treatment process for the first time.The as-obtained NFS-CNS600 features 3D interconnected ultra-thin carbon nanosheets with abundant active sites,tunable N/F/S species,and enlarged carbon interlayer spacing.The density functional theory calculation results demonstrate that NFS-CNSs exhibit the highest electron density and most negative K^(+)adsorption energy(-0.59 eV)compared to single or double-atom doping,thereby enhancing the storage performance of K+.As an anode for PIBs,the NFS-CNS600 exhibits good cycle stability(98.2%capacity retention after 200 cycles at 0.2 A g^(-1)),high capacity(409.1 mAh g^(-1) at 0.05 A g^(-1))and rate performance(179.5 mAh g^(-1) at 5 A g^(-1)).Besides,the NFS-CNS600 anode also displays outstanding sodium storage performance.This work offers a green strategy to synthesize CTP-based anode materials from coal chemical by-products for high-performance PIBs.展开更多
基金jointly funded by the National Natural Science Foundation of China(Grant Nos.42072178 and U2244207)the funding project of Northeast Geological S&T Innovation Center of China Geological Survey(Grant No.QCJJ2022-37)Geological Survey Project of China Geological Survey(Grant Nos.DD20190114,DD20230022,and DD20240045)。
文摘Organic-rich mudstones and shales,which hold significant potential for shale oil resources,characterize the first member of the Upper Cretaceous Qingshankou Formation(K_(2)qn~1)in the Sanzhao sag of the Songliao Basin,NE China.Focusing on 30 core samples obtained from the first shale oil parameter well,named SYY3 in the study area,we systematically analyzed the composition and stratigraphic distribution of the K_(2)qn~1 heteroatomic compounds using electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry(ESI FT-ICR MS),to assess their geological relevance to shale oil.The findings indicate that in the negative ion mode,the heteroatomic compounds predominantly consist of N_(1),N_(1)O_(1)-N_(1)O_(8),O_(1)-O_(8),O_(1)S_(1)-O_(6)S_(1);contrastingly,in the positive ion mode,they are primarily composed of N_(1)-N_(2),N_(1)O_(1)-N_(1)O_(4),N_(2)O_(1),O_(1)-O_(4),O_(1)S_(1)-O_(2)S_(1).Heteroatomic compound distributions vary significantly with depth in the negative ion mode,with minor variations in the positive ion mode.These distributions are categorized into three types based on the negative ion ratio((N_(1)+N_(1)O_(x))/O_(x)):TypeⅠ(>1.5),TypeⅡ(0.8-1.5),and TypeⅢ(<0.8);typesⅠandⅡgenerally exhibit a broader range of carbon numbers compared to TypeⅢ.The distribution of double bond equivalent(DBE)values across various sample types exhibits minimal variance,whereas that of carbon numbers shows substantial differences.Variations in heteroatomic compound compositions among the samples might have resulted from vertical sedimentary heterogeneity and differing biotic contributions.TypeⅢsamples show a decrease in total organic carbon(TOC)and free oil content(S_(1))compared to typesⅠandⅡ,but an increased oil saturation index(OSI),indicating a lower content of free oil but a higher proportion of movable oil.The reduced content of N-containing compounds implies lower paleolake productivity during deposition,leading to a reduction in TOC and S_(1).A lower TOC can enhance oil movability due to reduced oil adsorption,and the decreased presence of polar nitrogenous macromolecules with fewer highC-number heteroatomic compounds further promote shale oil movability.Additionally,the negative ion ratios of N1/N1O1and O2/O1 exhibit positive and negative correlations with the values of TOC,S_(1),and extractable organic matter(EOM),respectively,indicating that the salinity and redox conditions of the depositional water body are the primary controlling factors for both organic matter enrichment and shale oil accumulation.
基金financially supported by the National Key Research and Development Program of China(No.2021YFA1500800)the National Natural Science Foundation of China(Nos.51825204,52072377,521888101 and 51402199)+6 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2020192)the International Partnership Program of Chinese Academy of Sciences(No.174321KYSB20200005)China Postdoctoral Science Foundation(No.2017M621137)Liaoning Revitalization Talents Program(No.XLYC2007193)the Natural Science Foundation of Liaoning Province(Nos.2021-MS-014 and 2021NLTS1210)the University Innovation Talent Foundation of Liaoning Province(No.LR2018074)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(No.KF1708)。
文摘Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limit its PEC activity for water reduction.Here,we developed a heterostructure photocathode consisting of the Cu-doped NiO(Cu:NiO)hole selective layer(HSL)and Ni-doped CuFeO_(2)(Ni:CuFeO_(2))active layer by simply annealing a homogeneous Cu-Fe oxalate layer grown on the Ni film deposited on the fluorine doped tin oxide(FTO)substrate.The obtained heterostructure of Cu:NiO/Ni:CuFeO_(2) with enhanced charge carrier transportability and high-quality interface greatly promotes the separation of photogenerated carriers.Accordingly,the Cu:NiO/Ni:CuFeO_(2) photocathode exhibits a high photocurrent density of~0.9 mA·cm^(-2 )at 0.2 V(vs.reversible hydrogen electrode,RHE),outperforming most of the reported bare CuFeO_(2) photocathodes in the literature.And the photocurrent density can be further improved to 1.2 mA·cm^(-2) after decorating NiSx cocatalyst.
基金National key R&D Program of China(No.2022YFC3701903)natural science foundation of Shanxi Province(No.202203021211178)National Natural Science Foundation of China(51901209)for financial support.
文摘Solid-waste-based activated carbon(AC)was utilized as a carbon source to synthesize a series of carbon-based functional material RAC-X(X=P and S,where P and S denote phosphoric and sulfuric acids,respectively).The toluene adsorption capacities of the regeneration AC(RAC)samples can be significantly improved by adopting the heteroatomic modification strategy.RAC-P and RAC-S have the same specific surface area(1156 m^(2)/g)and similar porous structures.However,they have different toluene adsorption capacities,with 316.22 mg/g for RAC-P and 460.12 mg/g for RAC-S,which are 1.6 and 2.4 times greater than that for RAC.The X-ray photoelectron spectroscopy measurements showed that the increase in the amount ofπ–π^(2)chemical bond over the AC surface results in the improvement of the toluene adsorption performance.The density functional theory results showed that the S-containing functional groups loaded near the defect sites of RAC-S promote toluene adsorption.Moreover,reusability tests showed that RAC-S still retains 86%of its adsorption activity after four consecutive adsorption–desorption experiments.This indicates that the heteroatomic modification method affords excellent toluene adsorption performance and recycling practicability,which not only is beneficial for achieving the rational utilization of solid waste resources but also provides a practical method for the efficient elimination of volatile organic compounds.
基金the National Natural Science Foundation of China(No.52174283)the Shandong Provincial Natural Science Foundation(No.ZR2020MB044)Postgraduate Innovation Engineering Project of China University of Petroleum(East China)(No.YCX2021147).
文摘Although Fe-Ni combination performs well in transition metal-based oxygen evolution reaction(OER)electrocatalysts,there are lack of clear and general regulations mechanism to fully play the synergistic catalytic effect.Here,we made the utmost of the interaction of Fe–Ni heteroatomic pair to obtain a highly active Fe-Ni(oxy)hydroxide catalytic layer on iron foam(IF)and nickel foam(NF)by in-situ electrochemical deposition and rapid surface reconstruction,which only required 327 and 351 mV overpotential to provide a large current of 1,000 mA·cm^(−2),respectively.The results confirm that the moderate Ni-rich heteroatomic bonding(Ni–O–Fe–O–Ni)formed by adjusting the Ni/Fe ratio on the catalyst surface is important to offer predominant OER performance.Fe is a key component that enhances OER activity of Ni(O)OH,but Fe-rich structural surface formed by Fe–O–Ni–O–Fe bonding is not ideal.Finally,the remarkable oxygen evolution performance of the prepared Ni2Fe(O)OH/IF and FeNi2(O)OH/NF can be chalked up to the optimized electronic structure of Fe–Ni heteroatomic bonding,the efficient gas spillover,the fast electron transport,and nanosheet clusters morphology.In summary,our work suggests a comprehensive regulation mechanism for the construction of efficient Fe-Ni(oxy)hydroxide catalytic layer on inexpensive,stable,and self-supporting metallic material surface.
基金supported by the National Key R&D Program of China(Nos.2022YFB4101500 and 2022YFE0209500)the National Natural Science Foundation of China(Nos.22276191 and 21976177)the Qinghai Province Air Pollution Assessment and Fine Management Support Project,and the University of Chinese Academy of Science.
文摘As a potential adsorption material,it is still a challenge for activated carbon fiber(ACF)in efficient adsorption of ethanol due to its nonpolar surface,which is mainly emitted from the grain drying industry.This study prepared surface polarity-modified ACF using the heteroatom doping method.The modified ACF possessed a richer array of strongly polar oxygen/nitrogen-containing functional groups(primarily phenolic hydroxyl and lactone groups),a larger specific surface are1,and a more developed micropore structure.The adsorption capacities of ethanol for O-ACF and N-ACF were 4.110 mmol/g and 1.698 mmol/g,respectively,which were 11.3 times and 4.7 times those of unmodified ACF.This was a significant improvement over our previous work(0.363 mmol/g).The improvement of adsorption capacity for the N-ACF was mainly due to the higher specific surface are1,greater number of micropores(more adsorption sites)and abundant existence of defects,whereas,for O-ACF,the improvement mainly relied on the abundant presence of oxygen-containing functional groups on the surface.However,water had a negative effect on the adsorption of ethanol for the modified ACF due to competitive adsorption and the disappearance of capillary condensation.It was further revealed that the adsorption process of ethanol and water was quite different.It obeyed the linear driving force(LDF)model for ethanol adsorption,however,the intraparticle diffusion(IPD)model for water adsorption.
基金supported by the National Key Research and Development Program of China(No.2022YFA1602700 and 2022YFB2502104)the National Natural Science Foundation of China(22375089)the Key Research and Development Program of Jiangsu Provincial Department of Science and Technology of China(BE2022332).
文摘Electrocatalyst activity and stability demonstrate a“seesaw”relationship.Introducing vacancies(Vo)enhances the activity by improving reactant affinity and increasing accessible active sites.However,deficient or excessive Vo reduces polysulfide adsorption and lowers catalytic stability.Herein,a novel“heteroatoms synergistic anchoring vacancies”strategy is proposed to address the trade-off between high activity and stability.Phosphorus-doped CoSe_(2)with remained rich selenium vacancies(P-CS-Vo-0.5)was synthesized by producing abundant selenium Vo followed by controlled P atom doping.Atomic-scale microstructure analysis elucidated a dynamic process of surface vacancy generation and the subsequent partial occupation of these vacancies by P atoms.Density functional theory simulations and in situ Raman tests revealed that the Se vacancies provide highly active catalytic sites,accelerating polysulfide conversion,while P incorporation effectively reduces the surface energy of Se vacancies and suppresses their inward migration,enhancing structural robustness.The battery with the optimal P-CS-Vo-0.5 separator delivers an initial discharge capacity of 1306.7 mAh g^(-1)at 0.2C,and maintain 5.04 mAh cm^(-2)at a high sulfur loading(5.7 mg cm^(-2),5.0μL mg^(-1)),achieving 95.1%capacity retention after 80 cycles.This strategy of modifying local atomic environments offers a new route to designing highly active and stable catalysts.
基金financially supported by the National Natural Science Foundation of China(No.52202228,52402298)funded by the Science Research Project of Hebei Education Department(No.BJK2022011)+3 种基金the Central Funds Guiding the Local Science and Technology Development of Hebei Province(No.236Z4404G)the Beijing Tianjin Hebei Basic Research Cooperation Special Project(No.E2024202273)the Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)supported by the U.S.Department of Energy’s Office of Science,Office of Basic Energy Science,Materials Sciences and Engineering Division。
文摘Nickel-rich(Ni≥90%)layered oxides materials have emerged as a promising candidate for nextgeneration high-energy-density lithium-ion batteries(LIBs).However,their widespread application is hindered by structural fatigue and lattice oxygen loss.In this work,an epitaxial surface rock-salt nanolayer is successfully developed on the LiNi_(0.9)Co_(0.1)O_(2)sub-surface via heteroatom anchoring utilizing high-valence element molybdenum modification.This in-situ formed conformal buffer phase with a thickness of 1.2 nm effectively suppresses the continuous interphase side-reactions,and thus maintains the excellent structure integrity at high voltage.Furthermore,theoretical calculations indicate that the lattice oxygen reversibility in the anion framework of the optimized sample is obviously enhanced due to the higher content of O 2p states near the Fermi level than that of the pristine one.Meanwhile,the stronger Mo-O bond further reduces cell volume alteration,which improves the bulk structure stability of modified materials.Besides,the detailed charge compensation mechanism suggests that the average oxidation state of Ni is reduced,which induces more active Li+participating in the redox reactions,boosting the cell energy density.As a result,the uniquely designed cathode materials exhibit an extraordinary discharge capacity of 245.4 mAh g^(-1)at 0.1 C,remarkable rate performance of 169.3 mAh g^(-1)at 10 C at 4.5 V,and a high capacity retention of 70.5% after 1000 cycles in full cells at a high cut-off voltage of 4.4 V.This strategy provides an valuable insight into constructing distinctive heterostructure on highperformance Ni-rich layered cathodes for LIBs.
文摘The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.
基金funding support by the Changsha Natural Science Foundation(grant no.kq2208023)National Natural Scientific Foundation of China(grant no.12074113).
文摘Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe(oxy)hydroxide(Mn-NiFeOOH/LDH)heterojunction.Mn doping regulates heterojunction morphology(reducing nanoparticles and becoming thinner and denser nanosheets),Ni/Fe ratio and valence states(Ni^(2+),Ni^(3+),and Ni^(3+Δ))of Ni ions.The former could effectively increase surface active sites,and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction,en-abling more Ni^(2+)convert to Ni^(3+/3+Δ)that have higher intrinsic OER activity.As a result,the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm^(-2) and 296 mV@500 mA cm^(-2),and the improved OER performance are outdo to those of commercial RuO_(2) catalyst for OER.Moreover,the Mn-NiFeOOH/LDH affords the earliest initial potential(1.392 V vs.RHE),corresponds to a recorded low overpotential(162 mV).Based on the density functional theory(DFT),Mn dopants can alter intermedi-ate adsorption energy and effectively decrease∗OOH’s energy barrier.This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.
基金supported financially by the National Natural Science Foundation of China(No.52204069,No.22306171)the Natural Science Foundation of Zhejiang Province(No.LQ24B070005)the Jinhua Natural Science Foundation of China(2023-4-024)。
文摘Heavy oil,constituting a significant portion of global oil reserves,presents unique challenges in extraction and processing due to its high viscosity,largely influenced by asphaltenes and their heteroatom content.This study employs molecular dynamics(MD)simulations to investigate the selfaggregation and adsorption mechanisms of heteroatom/non-heteroatom asphaltenes,comparing linear and island structural configurations.Key findings reveal that linear heteroatom asphaltenes form dense,multi-layered aggregates,while island heteroatom asphaltenes exhibit stronger aggregation energy.On solid surfaces,linear asphaltenes display multi-layered adsorption,whereas island asphaltenes adopt a dispersed structure with higher adsorption energy,making them more resistant to removal.Compared to non-heteroatom asphaltenes,heteroatom asphaltenes significantly enhance the aggregation energy of the asphaltene itself and the interaction energy with light oil components,reducing the diffusion capacity of oil droplets and increasing viscosity.Although the viscosity of island heteroatom asphaltene oil drops is the largest,the role of heteroatom in linear asphaltene is more obvious,and linear heteroatom asphaltene and non-heteroatom show great differences in properties.Additionally,heteroatom-containing oil droplets exhibit stronger interactions with solid surfaces,driven by the influence of heteroatom asphaltenes on lighter oil components.These insights provide a deeper understanding of heavy oil viscosity mechanisms,offering a foundation for developing targeted viscosity-reduction strategies and optimizing heavy oil recovery and processing techniques.
基金National Natural Science Foundation of China (No. 22179123)Taishan Scholar Program of Shandong Province,China (No. tsqn202211048)Fundamental Research Funds for the Central Universities (No.202262010)。
文摘Zinc-ion hybrid capacitors (ZIHCs) have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental friendliness.However,their progress has been hampered by low energy and power density,as well as unsatisfactory long-cycle stability,mainly due to the lack of suitable electrode materials.In this context,we have developed manganese single atoms implanted in nitrogen-doped porous carbon nanosheets (MnSAs/NCNs) using a metal salt template method as cathodes for ZIHCs.The metal salt serves a dual purpose in the synthesis process:It facilitates the uniform dispersion of Mn atoms within the carbon matrix and acts as an activating agent to create the porous structure.When applied in ZIHCs,the MnSAs/NCNs electrode demonstrates exceptional performance,including a high capacity of 203 m Ah g^(-1),an energy density of 138 Wh kg^(-1)at 68 W kg^(-1),and excellent cycle stability with 91%retention over 10,000 cycles.Theoretical calculations indicate that the introduced Mn atoms modulate the local charge distribution of carbon materials,thereby improving the electrochemical property.This work demonstrates the significant potential of carbon materials with metal atoms in zinc-ion hybrid capacitors,not only in enhancing electrochemical performance but also in providing new insights and methods for developing high-performance energy storage devices.
基金supported by the financial support from the National Natural Science Foundation of China(Nos.22279046,22179053)Natural Science Excellent Youth Foundation of Jiangsu Province(No.BK20220112)Special Foundation for Carbon Peak Carbon Neutralization Technology Innovation Program of Jiangsu Province(No.BE2022026-2).
文摘Heterocyclic compounds play an important role in organic hole transport materials(HTMs)for perovskite solar cells(PSCs).Herein,a series of linear D-π-D HTMs(O-CBz,S-CBz,SO_(2)-CBz)with different dibenzoheterocycles core(dibenzofuran,dibenzothiophene,dibenzothiophene sulfone)were designed and synthesized,and their applications in PSCs were investigated.The intrinsic properties(CV,UV-vis,hole mobility and conductivity)were systematically investigated,demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs.Benefiting from the excellent hole mobility and conductivity,good film forming ability,and outstanding charge extraction and transport capability of S-CBz,FAPbI_(3)-based PSCs using S-CBz as HTM achieved a PCE of 25.0%,which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions(23.9%).Furthermore,due to the interaction between S and Pb^(2+),SCBz-based PSC devices exhibited improved stability.This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
基金supported by National Natural Science Foundation of China (No. 22006120)the Fundamental Research Funds for the Central Universities (No. SWU-XDJH202314)+1 种基金the Program for Innovation Team Building at Institutions of Higher Education in Chongqing (No. CXTDX201601011)Chongqing Municipal Natural Science Foundation (No. cstc2018jcyj AX0625)。
文摘Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-Co O/CP with doping strategy and heterostructure was synthesized for overall water splitting.The Ru/V-Co O exhibits excellent activity for HER and OER with low overpotentials of 49, 147 m V at a current density of 10 m A/cm^(2) in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 m A/cm^(2)current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial Ru O_(2)||Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts,providing new ideas for the design and development of efficient and stable electrocatalysts.
文摘Designing exceptional-performance and long-lasting oxygen reduction reaction(ORR)catalysts is a critical challenge for the development of rechargeable Zn-air batteries(ZABs).In this study,we introduce a metal-free ORR catalyst composed of F-N co-doped hollow carbon(FNC),specifically engineered to address the limitations of conventional catalysts.The FNC catalysts were synthesized using a template-assisted pyrolysis method,resulting in a hollow,porous architecture with a high specific surface area and numerous active sites.Concurrently,F doping optimized the electronic configuration of pyridinic nitrogen.The introduction of C-F bonds reduced the reaction energy barrier,and the resulting N-C-F configuration enhanced the stability of the nitrogen center.The catalyst exhibits outstanding ORR activity in alkaline media,exhibiting a half-wave potential(E_(1/2))of 0.87 V,surpassing that of commercial Pt/C(E_(1/2)=0.85 V).When applied to both aqueous and flexible ZAB configurations,the FNC catalyst achieved peak power densities of 172 and 85 mW cm^(-2),respectively,along with exceptional cycling stabilities exceeding 5300 and 302 h,respectively.This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs,particularly for use in flexible and wearable microelectronic devices.
基金Natural Science Foundation of Xinjiang Uygur Autonomous Region,Grant/Award Number:2023D01C11National Natural Science Foundation of China,Grant/Award Numbers:22369019,U2003216+2 种基金Special Projects on Regional Collaborative Innovation-SCO Science and Technology Partnership Program,International Science and Technology Cooperation Program,Grant/Award Number:2022E01020Tianshan Talent Training Program,Grant/Award Number:2023TSYCLJ0019National Key Research and Development Program of China,Grant/Award Numbers:2022YFB4101600,2022YFB4101601。
文摘The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.
基金financially supported by Yunnan Major Scientific and Technological Projects(No.202202AG050017-02)Yunnan Fundamental Research Projects(No.202101BE070001-017)the National Natural Science Foundation of China(Nos.52101258 and 52272202)
文摘The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalysts by Fe^(3+)etching during the hydrothermal and chemical deposition process.The as-prepared CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4 catalyst exhibits a lowoverpotential of 225 mV at 10 mA·cm^(-2)with a Tafel slope of 30.47 mV·dec^(-1).An overall water splitting electrolyzer(CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4‖Pt/C)is constructed,delivering a voltage of 1.48 V at a current density of10 mA·cm^(-2)with excellent durability.The dynamic phase evolution during the OER process is revealed by in situ Raman and XPS measurement,which represents that the introduced V and Fe ions facilitate the formation of active CoOOH as well as modify the electronic structure of the catalyst.Density functional theory(DFT)calculations further evidence that V and Fe introduction optimize the adsorption energies of oxygen intermediates*OH and*O,respectively,thereby enabling a synergistic optimization of the multi-step OER process and advancing electrocatalytic performance.
基金financially supported by the National Natural Science Foundation of China-Yunnan Joint Fund(U2002213)Science and Technology Talent and Platform Program of Yunnan Provincial Science and Technology Department(202305AM070001)+1 种基金the Xingdian Talent Program of Yunnan Provincethe Double-First Class University Plan(C176220100042).
文摘The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(ECR)frequently encounter high energy barriers and competitive hydrogen evolution reactions(HERs),which are urgent problems that need to be addressed.In this study,a catalyst(P100-Fe-N/C)with homogeneous P-tuned FeN_(2)binuclear sites(N_(2)PFe-FePN_(2))was successfully synthesised,demonstrating satisfactory performance in the ECR to CO.P100-Fe-N/C attains a peak FECOof 98.01%and a normalized TOF of 664.7 h-1at-0.7 VRHE,surpassing the performance of the Fe binuclear catalyst without P and singleatoms catalysts.In the MEA cell,a FECOexceeding 90%can still be achieved.Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system's energy.The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level,which facilitates the interaction of the catalyst with CO_(2),allowing more electrons to be injected into the CO_(2)molecule at the Fe binuclear sites and inhibiting the HER.The P-tuned FeN_(2)binuclear sites effectively lower the^(*)CO desorption barrier.
基金supported by the Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR124)。
文摘Heteroatom doping is a promising strategy for designing cost-effective and stable electrocatalysts toward the oxygen evolution reaction(OER),but the enhancement mechanism remains unclear.Herein,atomic Ir-O-Cu and Ir-O-Ir motifs are engineered into CuO nanowires via cation exchange and dehydration to elucidate the OER mechanism.Systematic characterizations confirm the atomic dispersion of Ir within the CuO lattice and the electron transfer from Ir to CuO while preserving the host structure.The asprepared single-atom Ir-doped CuO(IrSA-CuO),featuring predominant Cu-O-Ir motifs and coexisting IrO-Ir motifs,achieves a low OER overpotential of 204 mV at 10 mA cm^(-2)in 1 M KOH,coupled with a 69-fold higher mass activity than commercial IrO_(2).Furthermore,the Ir_(SA)-CuO maintains long-term stability for 300 h at 200 mA cm^(-2)with minimal overpotential alteration and an additional 120 h at500 mA cm^(-2)with overpotential increased by 15 mV.In situ Raman spectroscopy reveals that the Ir-O-Ir motifs suppress Cu^(Ⅱ) oxidation to Cu^(Ⅲ) by delaying the onset potential,enhancing the structural stability during OER.Density functional theory calculations demonstrate the Cu-O-Ir motifs lower the adsorption energy of bridged ^(*)O via asymmetric bonding,accelerating ^(*)OOH formation in the ratedetermining step.This work presents a heteroatom engineering strategy to balance electrocatalytic activity and durability,providing a blueprint for industrial electrocatalyst design.
基金financially supported by the National Natural Science Foundation of China(22478432,22108306,22178388)Taishan Scholars Program of Shandong Province(tsqn201909065)+2 种基金Shandong Provincial Natural Science Foundation(ZR2024JQ004)Innovation Fund Project for Graduate Student of China University of Petroleum(East China)the Fundamental Research Funds for the Central Universities(No.25CX04020A)。
文摘The development of single atom catalysts(SACs)with asymmetric active sites by defect regulation provides an encourage potential for oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER),but highly challenging.Herein,N-doped carbon(N-C)anchored atomically dispersed Ni-N_(3)site with proximity defects(Ni-N_(3)D)induced by Te atoms doping is reported.Benefitting from the inductive effect of proximity defect,the Ni-N_(3)D/Te-N-C catalyst performs excellent ORR and HER performance in alkaline and acid condition.Both in situ characterization and theoretical calculation reveal that the existence of proximity defect effect is conducive to lower rate-determining-step energy barrier of ORR and HER,thus accelerating the multielectron reaction kinetics.This work paves a novel strategy for constructing highactivity bifunctional SACs by defect engineering for development of sustainable energy.
基金the financial supports from the National Natural Science Foundation of China(Nos.52372037 and52072002)the Outstanding Scientific Research and Innovation Team Program of Higher Education Institutions of Anhui Province(No.2023AH010015)+1 种基金the Excellent Young Talents Fund Program of Higher Education Institutions of Anhui Province(No.2023AH030026)the financial support from the Anhui International Research Center of Energy Materials Green Manufacturing and Biotechnology.
文摘It is a big challenge to tune the structure and composition of carbon-based anode materials to increase the active sites by a green synthesis strategy for potassium ion batteries(PIBs).Herein,the N/F/S co-doped three-dimensional(3D)interconnected carbon nanosheets(NFS-CNSs)were synthesized from coal tar pitch(CTP)through a green and low-temperature treatment process for the first time.The as-obtained NFS-CNS600 features 3D interconnected ultra-thin carbon nanosheets with abundant active sites,tunable N/F/S species,and enlarged carbon interlayer spacing.The density functional theory calculation results demonstrate that NFS-CNSs exhibit the highest electron density and most negative K^(+)adsorption energy(-0.59 eV)compared to single or double-atom doping,thereby enhancing the storage performance of K+.As an anode for PIBs,the NFS-CNS600 exhibits good cycle stability(98.2%capacity retention after 200 cycles at 0.2 A g^(-1)),high capacity(409.1 mAh g^(-1) at 0.05 A g^(-1))and rate performance(179.5 mAh g^(-1) at 5 A g^(-1)).Besides,the NFS-CNS600 anode also displays outstanding sodium storage performance.This work offers a green strategy to synthesize CTP-based anode materials from coal chemical by-products for high-performance PIBs.
