Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperat...Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperatures and faces issues like low selectivity for liquid aromatics,separation difficulties,and rapid catalyst deactivation due to coking.To address this,a multifunctional Ni/HZSM-5 catalyst was developed to efficiently upgrade various polyolefins—including polyvinyl chloride—into gaseous alkanes(C_(1)–C_(5))and easily separable liquid aromatics(C_(6)–C_(12))at 400°C,without added solvents or hydrogen.Aromatic products make up 57.1 wt%of total output,with more than 97.8%selectivity for the liquid phase and a BTX(benzene,toluene,and xylene)selectivity of 76.1%.The high activity and selectivity for aromatics stem from synergistic interactions between Ni nanoparticles(NPs)and acid sites in the zeolite,which promote selective C–C bond breaking and control hydrogenolysis and aromatization pathways.This synergy allows precise control over the distribution of products by carbon number and favors the formation of separable aromatics.Notably,the catalyst also prevents coking by hydrogenolyzing and hydrogenating reactive intermediates before they form stable graphite-like deposits.Consequently,Ni/ZSM-5 catalyst demonstrates excellent stability,maintaining consistent aromatics yield over 13 consecutive cycles and processing over 30 times its weight in plastics without regeneration.After regeneration,the activity of the catalyst was fully restored,highlighting its potential for industrial use.This work offers valuable insights for designing durable,high-activity catalysts,providing a practical route to improve plastic recycling technologies.展开更多
Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formatio...Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formation)and metallic defects(Sn^(0)/Pb^(0)).In addition,the rapid and uncontrolled Sn^(2+)nucleation kinetics result in nonuniform crystallization.Herein,we introduce a natural redox shuttle glutathione(GSH)in Pb-Sn mixed PSCs,achieving regenerable antioxidation and crystallization regulation simultaneously.The reversible redox reactions between GSH and glutathione disulfide(GSSG)enable the self-healing of Sn^(4+)and Sn^(0)/Pb^(0)impurities,creating a regenerable antioxidation protective shell at the perovskite interfaces.Meanwhile,the strong coordination between GSH and perovskite regulates the crystallization process,optimizing the nucleation and crystallization kinetics.Furthermore,the GSH incorporation creates a high-quality charge separation junction at the perovskite/hole transport layer,facilitating carrier separation and extraction.The optimized Pb-Sn PSCs exhibit impressive power conversion efficiencies(PCEs)of up to 23.71%.The champion all-perovskite tandem PSCs with GSH achieve a PCE of 28.49%and retain 90%of the initial PCE after 560 h of continuous illumination.This work establishes a new nature-inspired redox shuttling strategy and elucidates its working mechanism,advancing the development of efficient and stable all-perovskite tandem solar cells.展开更多
The self-assembled monolayer(SAM),functioning as a hole transport layer,holds the potential to substantially elevate the efficiency of perovskite and organic solar cells.Nevertheless,incomplete SAM coverage may result...The self-assembled monolayer(SAM),functioning as a hole transport layer,holds the potential to substantially elevate the efficiency of perovskite and organic solar cells.Nevertheless,incomplete SAM coverage may result in interface defects lurking between the photovoltaic layer and the electrode,thereby causing non-radiative recombination losses of interfacial charges.To tackle this issue,we introduced 4-bromobutyric acid to co-assemble with the SAM,yielding a more compact co-assembled monolayer(co-SAM)that effectively repairs these defective zones.Confocal laser scanning microscopy and Kelvin Probe Force Microscopy show that co-SAMs successfully mitigate interface defects in the previously uncovered electrode regions.Furthermore,the work function of the electrodes is elevated to 5.6 eV,facilitating efficient hole extraction.Consequently,devices incorporating co-SAMs exhibit notably reduced non-radiative recombination losses.The power conversion efficiency(PCE)of the devices is enhanced to 20.0% in binary organic solar cells,and an even more remarkable breakthrough PCE of 25.8% is achieved in perovskite/organic tandem devices.This study introduces a straightforward strategy to improve the hole-selective contact of electrodes,ultimately boosting the overall efficiency of the devices.展开更多
The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexit...The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.展开更多
Recent progress in inverted perovskite solar cells(i PSCs)highlights the critical role of interface engineering between the charge transport layer and perovskite.Self-assembled monolayers(SAM)on transparent conductive...Recent progress in inverted perovskite solar cells(i PSCs)highlights the critical role of interface engineering between the charge transport layer and perovskite.Self-assembled monolayers(SAM)on transparent conductive oxide electrodes serve effectively as hole transport layers,though challenges such as energy mismatches and surface inhomogeneities remain.Here,a blended self-assembled monolayer of(2-(9H-carbazol-9-yl)ethyl)phosphonic acid(2PACz)and(4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl)phosphonic acid(Me-4PACz)is developed,offering improved surface potential uniformity and interfacial energy alignment compared to individual SAMs.Interactions between the SAMs and ionic species are investigated with simulation analysis conducted,revealing the elimination of interfacial energy barriers through precise energy-level tuning.This strategy enables wide-bandgap(1.67 e V)perovskite solar cells with inverted structures with over 24%efficiency,an open-circuit voltage(V_(oc))of 1.268 V,and a certified fill factor(FF)of 86.8%,leading to a certified efficiency of 23.42%.The approach also enables high-efficiency semi-transparent devices and a mechanically stacked four-terminal perovskite/silicon tandem solar cell reaching 30.97%efficiency.展开更多
A major challenge for n-i-p structured perovskite/silicon tandem solar cells(TSCs)is the use of 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene(spiro-OMe TAD),a commonly used hole transport la...A major challenge for n-i-p structured perovskite/silicon tandem solar cells(TSCs)is the use of 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene(spiro-OMe TAD),a commonly used hole transport layer,which induces significant optical losses and consequently reduces device current.Herein,we propose an ultra-thin(10 nm)vacuum thermal evaporation(VTE)-deposited spiro-OMe TAD,coupled with a 2D/3D perovskite heterojunction,to simultaneously enhance the optical and electrical properties of n-i-p perovskite/silicon TSCs.Our results demonstrate that the 10-nm-thick spiro-OMe TAD layer significantly improves optical performance,achieving a 92.2% reduction in parasitic absorption and an 18.4%decrease in reflection losses.Additionally,the incorporation of the 2D/3D perovskite heterojunction facilitates improved molecular arrangement and enhanced surface uniformity of the ultrathin spiro-OMe TAD,leading to higher tolerance to interface defects and more efficient hole extraction.Consequently,n-i-p perovskite/silicon TSCs featuring ultrathin spiro-OMe TAD exhibit remarkable efficiencies of 29.73%(0.135 cm^(2))and 28.77%(28.25% certified efficiency,1.012 cm^(2)),along with improved stability.展开更多
[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid(Me-4PACz)self-assembled monolayer(SAM)as the hole transport materials have been demonstrated remarkable potential in perovskite solar cells(PSCs).However,the hyd...[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid(Me-4PACz)self-assembled monolayer(SAM)as the hole transport materials have been demonstrated remarkable potential in perovskite solar cells(PSCs).However,the hydrophobicity of Me-4PACz presents a critical challenge for the fabrication of high-quality perovskite films due to its poor wettability.Here,a doped Al_(2)O_(3)with Me-4PACz to modify the Me-4PACz surface was proposed.On one hand,this approach improved the wettability of the Me-4PACz film,enhancing the coverage,uniformity,and buried interface properties of the perovskite film.On the other hand,compared to Al_(2)O_(3)modification alone,doping Al_(2)O_(3)with Me-4PACz allowed direct contact between the perovskite and Me-4PACz,resulting in better buried interface passivation.As a result,we achieved an efficiency of 22.71%for single-junction wide-bandgap perovskite solar cells(1.68 eV).Additionally,the efficiency of perovskite/silicon tandem solar cells was improved from 28.68%to 30.92%,with a significant reduction in hysteresis.Furthermore,the tandem cells demonstrated no degradation after 4200 s of operation at the maximum power point.展开更多
The CO_(2)-assisted oxidative dehydrogenation of ethane(CO_(2)-ODHE)provides a promising way to produce ethylene and utilize CO_(2).Simultaneous upgrading of ethane into the high value-added chemical products and the ...The CO_(2)-assisted oxidative dehydrogenation of ethane(CO_(2)-ODHE)provides a promising way to produce ethylene and utilize CO_(2).Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO_(2)emissions could be achieved.However,the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts.In this paper,ZnO-doped ZrO_(2)bifunctional catalysts(Zn_(x)ZrO)with different Zn/Zr molar ratios were prepared by the deposition-precipitation method,and the functions of various sites for CO_(2)-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment:the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene,while the more oxygen vacancies(OV)created by the introduction of Zn^(2+)are responsible for the efficient activation C=O bonds of CO_(2),thus promoting the RWGS reaction.In addition,the Zn0.2ZrO catalyst demonstrated excellent catalytic performances,with C_(2)H_(6)conversion,C_(2)H_(4)yield,and CO_(2)conversion about 19.1%,10.5%,and 10.6%within 5 h,respectively(600℃,GHSV=3000 mL/(g·h)).Especially,the initial ethylene space-time yield of 355.5μmol/(min·g)was obtained under 6000 mL/(g·h);Finally,the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.展开更多
Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified...Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified MCM-22 zeolite combined with ZnCeZrOx solid solution is reported to catalyze the tandem CO_(2)hydrogenation and toluene methylation reaction at a relatively low temperature(<603 K),showing xylene selectivity of 92.4%and PX selectivity of 62%(PX/X,67%)in total aromatics at a CO_(2)conversion of 7.7%,toluene conversion of 23.6%and low CO selectivity of 11.6%,as well as giving high STY of xylene(302.0 mg·h^(–1)·gcat^(–1))and PX(201.6 mg·h^(–1)·gcat^(–1)).The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22,which promoted zeolite shape-selectivity and suppressed secondary reactions.展开更多
The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of me...The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift(RWGS)reaction.Herein,we present a novel approach for the synthesis of CH_(3)OH via photocatalytic CO_(2) hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy(OV)-rich molybdenum dioxide(MoO_(2)),resulting in a remarkable selectivity of 43.78%.The active sites in the Au/MoO_(2) catalyst are high-density Au-oxygen vacancies,which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation.This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO_(2) to CH_(3)OH.展开更多
Solar energy, as a renewable resource, is an effective solution to the current global energy shortage problem. To actively respond to the call for "carbon peak" and "carbon neutrality", solar cell ...Solar energy, as a renewable resource, is an effective solution to the current global energy shortage problem. To actively respond to the call for "carbon peak" and "carbon neutrality", solar cell industry has experienced unprecedented development. The full utilization of solar energy resources remains an urgent issue to be addressed.展开更多
All-perovskite tandem solar cells(ATSCs) have the potential to surpass the Shockley-Queisser efficiency limit of conventional single-junction devices. However, the performance and stability of mixed tin–lead(Sn–Pb) ...All-perovskite tandem solar cells(ATSCs) have the potential to surpass the Shockley-Queisser efficiency limit of conventional single-junction devices. However, the performance and stability of mixed tin–lead(Sn–Pb) perovskite solar cells(PSCs), which are crucial components of ATSCs, are much lower than those of lead-based perovskites. The primary challenges include the high crystallization rate of perovskite materials and the susceptibility of Sn^(2+) oxidation, which leads to rough morphology and unfavorable p-type self-doping. To address these issues, we introduced ethylhydrazine oxalate(EDO) at the perovskite interface, which effectively inhibits the oxidation of Sn^(2+) and simultaneously enhances the crystallinity of the perovskite. Consequently, the EDO-modified mixed tin-lead PSCs reached a power conversion efficiency(PCE) of 21.96% with high reproducibility. We further achieved a 27.58% efficient ATSCs by using EDO as interfacial passivator in the Sn-Pb PSCs.展开更多
This study first demonstrates the potential of organic photoabsorbing blends in overcoming a critical limitation of metal oxide photoanodes in tandem modules:insufficient photogenerated current.Various organic blends,...This study first demonstrates the potential of organic photoabsorbing blends in overcoming a critical limitation of metal oxide photoanodes in tandem modules:insufficient photogenerated current.Various organic blends,including PTB7-Th:FOIC,PTB7-Th:O6T-4F,PM6:Y6,and PM6:FM,were systematically tested.When coupled with electron transport layer(ETL)contacts,these blends exhibit exceptional charge separation and extraction,with PM6:Y6 achieving saturation photocurrents up to 16.8 mA cm^(-2) at 1.23 VRHE(oxygen evolution thermodynamic potential).For the first time,a tandem structure utilizing organic photoanodes has been computationally designed and fabricated and the implementation of a double PM6:Y6 photoanode/photovoltaic structure resulted in photogenerated currents exceeding 7mA cm^(-2) at 0 VRHE(hydrogen evolution thermodynamic potential)and anodic current onset potentials as low as-0.5 VRHE.The herein-presented organic-based approach paves the way for further exploration of different blend combinations to target specific oxidative reactions by selecting precise donor/acceptor candidates among the multiple existing ones.展开更多
Short tandem repeats(STRs)modulate gene expression and contribute to trait variation.However,a systematic evaluation of the genomic characteristics of STRs has not been conducted,and their influence on gene expression...Short tandem repeats(STRs)modulate gene expression and contribute to trait variation.However,a systematic evaluation of the genomic characteristics of STRs has not been conducted,and their influence on gene expression in rice remains unclear.Here,we construct a map of 137,629 polymorphic STRs in the rice(Oryza sativa L.)genome using a population-scale resequencing dataset.A genome-wide survey encompassing 4726 accessions shows that the occurrence frequency,mutational patterns,chromosomal distribution,and functional properties of STRs are correlated with the sequences and lengths of repeat motifs.Leveraging a transcriptome dataset from 127 rice accessions,we identify 44,672 expression STRs(eSTRs)by modeling gene expression in response to the length variation of STRs.These eSTRs are notably enriched in the regulatory regions of genes with active transcriptional signatures.Population analysis identifies numerous STRs that have undergone genetic divergence among different rice groups and 1726 tagged STRs that may be associated with agronomic traits.By editing the(ACT)_(7) STR in OsFD1 promoter,we further experimentally validate its role in regulating gene expression and phenotype.Our study highlights the contribution of STRs to transcriptional regulation in plants and establishes the foundation for their potential use as alternative targets for genetic improvement.展开更多
Traditional electrospray ionization tandem mass spectrometry(ESI-MS^(n))has been a powerful tool in diverse research areas,however,it faces great limitations in the study of protein-small molecule interactions.In this...Traditional electrospray ionization tandem mass spectrometry(ESI-MS^(n))has been a powerful tool in diverse research areas,however,it faces great limitations in the study of protein-small molecule interactions.In this article,the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry(TC-ESI-MS^(n))is applied to investigate interactions between ubiquitin and two flavonol molecules,respectively.The combination of collision-induced dissociation(CID)and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges.While structural changes of proteins disturbed by small molecules are unseen in ESI-MS^(n),TC-ESI-MS^(n)allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions,meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data,and the characteristics of structural intermediates.展开更多
Tandem solar cells(TSCs)represent an attractive technology that can overcome the single-junction Shockdey-Queisser limit.Recently,a tandem structure combining wide-bandgap metal halide perovskite with complementary ba...Tandem solar cells(TSCs)represent an attractive technology that can overcome the single-junction Shockdey-Queisser limit.Recently,a tandem structure combining wide-bandgap metal halide perovskite with complementary bandgap copper indium gallium selenide(CIGS)photovoltaic technology has demonstrated a realistic pathway to achieve the industrialization goal of pushing power conversion efficiency(PCE)approaching 30% at low-cost.In this review,we first pinpoint the unique advantage of perovskite/CIGS tandems with respect to the other mainstream photovoltaic technologies and retrospect the research progress of perovskite/CIGS TSCs from both PCE and stability perspective in the last years.Next,we comprehensively discuss the major advancements in absorbers,functional layers of the individual sub-cell,and the interconnection layer between them in the recent decade.Finally,we outline several essential scientific and engineering challenges that are to be solved toward the development of efficient,long-term stable,and large-area perovskite/CIGS TSCs in the future.展开更多
All-perovskite tandem solar cells have the potential to surpass the theoretical efficiency limit of single junction solar cells by reducing thermalization losses.However,the challenges encompass the oxidation of Sn^(2...All-perovskite tandem solar cells have the potential to surpass the theoretical efficiency limit of single junction solar cells by reducing thermalization losses.However,the challenges encompass the oxidation of Sn^(2+)to Sn^(4+)and uncontrolled crystallization kinetics in Sn-Pb perovskites,leading to nonradiative recombination and compositional heterogeneity to decrease photovoltaic efficiency and operational stability.Herein,we introduced an ionic liquid additive,1-ethyl-3-methylimidazolium iodide (EMIMI) into Sn-Pb perovskite precursor to form low-dimensional Sn-rich/pure-Sn perovskites at grain boundaries,which mitigates oxidation of Sn^(2+)to Sn^(4+)and regulates the film-forming dynamics of Sn/Pb-based perovskite films.The optimized single-junction Sn-Pb perovskite devices incorporating EMIMI achieved a high efficiency of 22.87%.Furthermore,combined with wide-bandgap perovskite sub-cells in tandem device,we demonstrate 2-terminal all-perovskite tandem solar cells with a power conversion efficiency of 28.34%,achieving improved operational stability.展开更多
Mesoporous framework supported metal nanoparticle catalyst represents a promising material platform for creating multiple active sites that drive tandem reactions. In this study, we demonstrate a novel catalyst design...Mesoporous framework supported metal nanoparticle catalyst represents a promising material platform for creating multiple active sites that drive tandem reactions. In this study, we demonstrate a novel catalyst design that involves the encapsulation of CuNi alloy nanoparticles within mesoporous silicon carbide nanofibers (mSiC_(f)) to achieve efficient tandem conversion of furfural (FFA) into 2-(isopropoxymethyl)furan (IPF). The unique one-dimensional (1D) mesoporous structure of mSiC_(f), coupled with abundant oxygen-containing groups, offers a favorable surface microenvironment for the stabilization of bimetallic CuNi active sites. Through carefully optimizing metal to acid sites, we have developed a catalyst containing a total mass ratio of 20 % Cu and Ni, which exhibits a remarkable performance with complete FFA conversion and 92 % IPF selectivity in 4 h. In-depth mechanistic investigations have revealed that the superior activity of this catalyst is attributed to a tandem reaction mechanism. Initially, FFA is hydrogenated at the dual metal active sites to produce furfuryl alcohol (FOL) as an intermediate, which is subsequently etherified at the acid sites with suitable species and strengths on the mSiC_(f) supports. Additionally, the robust 1D mSiC_(f) framework effectively protects the metal sites from agglomeration, resulting in excellent reusability of the catalyst. This study underscores the potential of mesoporous silicon carbide-supported bimetallic active sites for achieving enhanced tandem catalytic functionality.展开更多
The development of high-voltage tandem thin-film supercapacitors(TFSCs)has been limited by the issues such as expensive electrode materials,indispensable commercial separators and metal current collectors,and complex ...The development of high-voltage tandem thin-film supercapacitors(TFSCs)has been limited by the issues such as expensive electrode materials,indispensable commercial separators and metal current collectors,and complex manufacturing processes.Herein,we develop a potentially scalable approach to address all these issues by using CO_(2) laser pyrolysis of polyimide(PI)paper into the three-dimensional(3D)morphology of graphene paper in air.The formation process and mechanism of PI to graphene were clarified by microstructure and chemical characterizations and reaction molecular dynamics.The influences of laser scan density,power,defocus,and scan speed on the sheet resistance,longitudinal resistance,Raman spectra,and electrochemical performance of graphene papers were systematically investigated.Results indicate that high-quality graphene papers with ultralow sheet resistance(4.88Ω·square^(-1))and longitudinal resistance(3.46Ω)and extra-large crystalline size(96.1 nm)were achieved under optimized process parameters.The graphene papers can simultaneously serve as active electrode materials,current collectors,and interconnectors.The active area of electrodes is defined by a PI mask,with the help of which a hydrogel electrolyte functions as a separator.The assembled graphene paper-based TFSCs demonstrate outstanding electrochemical performance and mechanical flexibility,with the areal capacitance of 54.5 mF·cm^(-2),energy density of 10.9µWh·cm^(-2),and cycle stability retention of 86.9%over 15000 cycles.Moreover,all the tandem metal-free TFSCs,ranging from 1 to 160 cells,show excellent performance uniformity.The output voltage increases linearly from 1.2 V to 200 V.Significantly,the 160-tandem TFSCs exhibit a high voltage density within a compact volume of∼3.8 cm^(3).This work provides an avenue for achieving tandem metal-free TFSCs in a simple and efficient manner.展开更多
基金supported by the National Key R&D Program of China(2021YFA1501700)the National Natural Science Foundation of China(22272114)+2 种基金the Funding for Hundred Talent Program(20822041E4079)the Fundamental Research Funds from Sichuan University(2022SCUNL103)This work has also been supported by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.via collaborative project No.36800000-24-ZC0607-0175.
文摘Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperatures and faces issues like low selectivity for liquid aromatics,separation difficulties,and rapid catalyst deactivation due to coking.To address this,a multifunctional Ni/HZSM-5 catalyst was developed to efficiently upgrade various polyolefins—including polyvinyl chloride—into gaseous alkanes(C_(1)–C_(5))and easily separable liquid aromatics(C_(6)–C_(12))at 400°C,without added solvents or hydrogen.Aromatic products make up 57.1 wt%of total output,with more than 97.8%selectivity for the liquid phase and a BTX(benzene,toluene,and xylene)selectivity of 76.1%.The high activity and selectivity for aromatics stem from synergistic interactions between Ni nanoparticles(NPs)and acid sites in the zeolite,which promote selective C–C bond breaking and control hydrogenolysis and aromatization pathways.This synergy allows precise control over the distribution of products by carbon number and favors the formation of separable aromatics.Notably,the catalyst also prevents coking by hydrogenolyzing and hydrogenating reactive intermediates before they form stable graphite-like deposits.Consequently,Ni/ZSM-5 catalyst demonstrates excellent stability,maintaining consistent aromatics yield over 13 consecutive cycles and processing over 30 times its weight in plastics without regeneration.After regeneration,the activity of the catalyst was fully restored,highlighting its potential for industrial use.This work offers valuable insights for designing durable,high-activity catalysts,providing a practical route to improve plastic recycling technologies.
基金supported by Guangdong Basic and Applied Basic Research Foundation(2025A1515011362)the National Natural Science Foundation of China(52102304,52172238)Open Project of Shaanxi Laboratory of Aerospace Power(2021SXSYS-01-03).
文摘Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formation)and metallic defects(Sn^(0)/Pb^(0)).In addition,the rapid and uncontrolled Sn^(2+)nucleation kinetics result in nonuniform crystallization.Herein,we introduce a natural redox shuttle glutathione(GSH)in Pb-Sn mixed PSCs,achieving regenerable antioxidation and crystallization regulation simultaneously.The reversible redox reactions between GSH and glutathione disulfide(GSSG)enable the self-healing of Sn^(4+)and Sn^(0)/Pb^(0)impurities,creating a regenerable antioxidation protective shell at the perovskite interfaces.Meanwhile,the strong coordination between GSH and perovskite regulates the crystallization process,optimizing the nucleation and crystallization kinetics.Furthermore,the GSH incorporation creates a high-quality charge separation junction at the perovskite/hole transport layer,facilitating carrier separation and extraction.The optimized Pb-Sn PSCs exhibit impressive power conversion efficiencies(PCEs)of up to 23.71%.The champion all-perovskite tandem PSCs with GSH achieve a PCE of 28.49%and retain 90%of the initial PCE after 560 h of continuous illumination.This work establishes a new nature-inspired redox shuttling strategy and elucidates its working mechanism,advancing the development of efficient and stable all-perovskite tandem solar cells.
基金supported by the National Natural Science Foundation of China(52303239,51933001,22475114)the Natural Science Foundation of Shandong Province(ZR2022QB141,2023HWYQ-087)+1 种基金the Shanghai Pujiang Program(23PJ1409700)the Hubei Province Key Research Program(2023BAB109)。
文摘The self-assembled monolayer(SAM),functioning as a hole transport layer,holds the potential to substantially elevate the efficiency of perovskite and organic solar cells.Nevertheless,incomplete SAM coverage may result in interface defects lurking between the photovoltaic layer and the electrode,thereby causing non-radiative recombination losses of interfacial charges.To tackle this issue,we introduced 4-bromobutyric acid to co-assemble with the SAM,yielding a more compact co-assembled monolayer(co-SAM)that effectively repairs these defective zones.Confocal laser scanning microscopy and Kelvin Probe Force Microscopy show that co-SAMs successfully mitigate interface defects in the previously uncovered electrode regions.Furthermore,the work function of the electrodes is elevated to 5.6 eV,facilitating efficient hole extraction.Consequently,devices incorporating co-SAMs exhibit notably reduced non-radiative recombination losses.The power conversion efficiency(PCE)of the devices is enhanced to 20.0% in binary organic solar cells,and an even more remarkable breakthrough PCE of 25.8% is achieved in perovskite/organic tandem devices.This study introduces a straightforward strategy to improve the hole-selective contact of electrodes,ultimately boosting the overall efficiency of the devices.
基金supported financially by the Key Project of the National Ministry of Science and Technology (No.2022YFC3705005)the Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering,MOE (KLIEEE-22-05)
文摘The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.
文摘Recent progress in inverted perovskite solar cells(i PSCs)highlights the critical role of interface engineering between the charge transport layer and perovskite.Self-assembled monolayers(SAM)on transparent conductive oxide electrodes serve effectively as hole transport layers,though challenges such as energy mismatches and surface inhomogeneities remain.Here,a blended self-assembled monolayer of(2-(9H-carbazol-9-yl)ethyl)phosphonic acid(2PACz)and(4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl)phosphonic acid(Me-4PACz)is developed,offering improved surface potential uniformity and interfacial energy alignment compared to individual SAMs.Interactions between the SAMs and ionic species are investigated with simulation analysis conducted,revealing the elimination of interfacial energy barriers through precise energy-level tuning.This strategy enables wide-bandgap(1.67 e V)perovskite solar cells with inverted structures with over 24%efficiency,an open-circuit voltage(V_(oc))of 1.268 V,and a certified fill factor(FF)of 86.8%,leading to a certified efficiency of 23.42%.The approach also enables high-efficiency semi-transparent devices and a mechanically stacked four-terminal perovskite/silicon tandem solar cell reaching 30.97%efficiency.
基金supported by the National Key Research and Development Program of China(Grant No.2024YFB3817304)the National Natural Science Foundation of China(Grant No.61874177)+4 种基金Zhejiang Provincial Natural Science Foundation of China(Grant No.LQN25F040009)Ningbo Natural Science Foundation(Grant No.2024J226)China Postdoctoral Science Foundation(Grant No.GZB20230787,2024M753344)Baima Lake Laboratory Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(Grant No.LBMHD24E020002)Key Research and Development Program of Ningbo(Grant No.2023Z151)。
文摘A major challenge for n-i-p structured perovskite/silicon tandem solar cells(TSCs)is the use of 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene(spiro-OMe TAD),a commonly used hole transport layer,which induces significant optical losses and consequently reduces device current.Herein,we propose an ultra-thin(10 nm)vacuum thermal evaporation(VTE)-deposited spiro-OMe TAD,coupled with a 2D/3D perovskite heterojunction,to simultaneously enhance the optical and electrical properties of n-i-p perovskite/silicon TSCs.Our results demonstrate that the 10-nm-thick spiro-OMe TAD layer significantly improves optical performance,achieving a 92.2% reduction in parasitic absorption and an 18.4%decrease in reflection losses.Additionally,the incorporation of the 2D/3D perovskite heterojunction facilitates improved molecular arrangement and enhanced surface uniformity of the ultrathin spiro-OMe TAD,leading to higher tolerance to interface defects and more efficient hole extraction.Consequently,n-i-p perovskite/silicon TSCs featuring ultrathin spiro-OMe TAD exhibit remarkable efficiencies of 29.73%(0.135 cm^(2))and 28.77%(28.25% certified efficiency,1.012 cm^(2)),along with improved stability.
基金supported by the National Key Research and Development Program of China(2023YFB4202503)the cooperation project between Three Gorges Corporation and Nankai University(202103571)+6 种基金the National Natural Science Foundation Joint Fund(U21A2072)the National Science Foundation(62274099,62104115)Tianjin Science and Technology Project(24ZXZSSS00160)Yunnan Provincial Science and Technology Project at Southwest United Graduate School(202302A0370009)the China Higher Education Discipline Innovation Overseas Expert Introduction Project(B16027)the Haihe Laboratory of Sustainable Chemical Transformationsthe Fundamental Research Funds for the Central Universities,Nankai University。
文摘[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid(Me-4PACz)self-assembled monolayer(SAM)as the hole transport materials have been demonstrated remarkable potential in perovskite solar cells(PSCs).However,the hydrophobicity of Me-4PACz presents a critical challenge for the fabrication of high-quality perovskite films due to its poor wettability.Here,a doped Al_(2)O_(3)with Me-4PACz to modify the Me-4PACz surface was proposed.On one hand,this approach improved the wettability of the Me-4PACz film,enhancing the coverage,uniformity,and buried interface properties of the perovskite film.On the other hand,compared to Al_(2)O_(3)modification alone,doping Al_(2)O_(3)with Me-4PACz allowed direct contact between the perovskite and Me-4PACz,resulting in better buried interface passivation.As a result,we achieved an efficiency of 22.71%for single-junction wide-bandgap perovskite solar cells(1.68 eV).Additionally,the efficiency of perovskite/silicon tandem solar cells was improved from 28.68%to 30.92%,with a significant reduction in hysteresis.Furthermore,the tandem cells demonstrated no degradation after 4200 s of operation at the maximum power point.
文摘The CO_(2)-assisted oxidative dehydrogenation of ethane(CO_(2)-ODHE)provides a promising way to produce ethylene and utilize CO_(2).Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO_(2)emissions could be achieved.However,the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts.In this paper,ZnO-doped ZrO_(2)bifunctional catalysts(Zn_(x)ZrO)with different Zn/Zr molar ratios were prepared by the deposition-precipitation method,and the functions of various sites for CO_(2)-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment:the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene,while the more oxygen vacancies(OV)created by the introduction of Zn^(2+)are responsible for the efficient activation C=O bonds of CO_(2),thus promoting the RWGS reaction.In addition,the Zn0.2ZrO catalyst demonstrated excellent catalytic performances,with C_(2)H_(6)conversion,C_(2)H_(4)yield,and CO_(2)conversion about 19.1%,10.5%,and 10.6%within 5 h,respectively(600℃,GHSV=3000 mL/(g·h)).Especially,the initial ethylene space-time yield of 355.5μmol/(min·g)was obtained under 6000 mL/(g·h);Finally,the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.
文摘Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified MCM-22 zeolite combined with ZnCeZrOx solid solution is reported to catalyze the tandem CO_(2)hydrogenation and toluene methylation reaction at a relatively low temperature(<603 K),showing xylene selectivity of 92.4%and PX selectivity of 62%(PX/X,67%)in total aromatics at a CO_(2)conversion of 7.7%,toluene conversion of 23.6%and low CO selectivity of 11.6%,as well as giving high STY of xylene(302.0 mg·h^(–1)·gcat^(–1))and PX(201.6 mg·h^(–1)·gcat^(–1)).The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22,which promoted zeolite shape-selectivity and suppressed secondary reactions.
文摘The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift(RWGS)reaction.Herein,we present a novel approach for the synthesis of CH_(3)OH via photocatalytic CO_(2) hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy(OV)-rich molybdenum dioxide(MoO_(2)),resulting in a remarkable selectivity of 43.78%.The active sites in the Au/MoO_(2) catalyst are high-density Au-oxygen vacancies,which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation.This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO_(2) to CH_(3)OH.
文摘Solar energy, as a renewable resource, is an effective solution to the current global energy shortage problem. To actively respond to the call for "carbon peak" and "carbon neutrality", solar cell industry has experienced unprecedented development. The full utilization of solar energy resources remains an urgent issue to be addressed.
基金financially supported by National Key R&D Program of China (2025YFE0100300)the National Natural Science Foundation of China (52202293 and 52330004)the Fundamental Research Funds for the Central Universities (WUT: 2023IVA075 and 2023IVB009)。
文摘All-perovskite tandem solar cells(ATSCs) have the potential to surpass the Shockley-Queisser efficiency limit of conventional single-junction devices. However, the performance and stability of mixed tin–lead(Sn–Pb) perovskite solar cells(PSCs), which are crucial components of ATSCs, are much lower than those of lead-based perovskites. The primary challenges include the high crystallization rate of perovskite materials and the susceptibility of Sn^(2+) oxidation, which leads to rough morphology and unfavorable p-type self-doping. To address these issues, we introduced ethylhydrazine oxalate(EDO) at the perovskite interface, which effectively inhibits the oxidation of Sn^(2+) and simultaneously enhances the crystallinity of the perovskite. Consequently, the EDO-modified mixed tin-lead PSCs reached a power conversion efficiency(PCE) of 21.96% with high reproducibility. We further achieved a 27.58% efficient ATSCs by using EDO as interfacial passivator in the Sn-Pb PSCs.
基金partly funded by a BIST Ignite Programme grant from the Barcelona Institute of Science and Technology(Code:MOLOPEC)financial support from LICROX and SOREC2 EUFunded projects(Codes:951843 and 101084326)+7 种基金the BIST Program,and Severo Ochoa Programpartially funded by CEX2019-000910-S(MCIN/AEI/10.13039/501100011033 and PID2020-112650RBI00),Fundació Cellex,Fundació Mir-PuigGeneralitat de Catalunya through CERCAfunding from the European Union’s Horizon Europe research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101081441financial support by the Agencia Estatal de Investigación(grant PRE2018-084881)the financial support by from the European Union’s Horizon Europe research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101081441support from the MCIN/AEI JdC-F Fellowship(FJC2020-043223-I)the Severo Ochoa Excellence Postdoctoral Fellowship(CEX2019-000910-S).
文摘This study first demonstrates the potential of organic photoabsorbing blends in overcoming a critical limitation of metal oxide photoanodes in tandem modules:insufficient photogenerated current.Various organic blends,including PTB7-Th:FOIC,PTB7-Th:O6T-4F,PM6:Y6,and PM6:FM,were systematically tested.When coupled with electron transport layer(ETL)contacts,these blends exhibit exceptional charge separation and extraction,with PM6:Y6 achieving saturation photocurrents up to 16.8 mA cm^(-2) at 1.23 VRHE(oxygen evolution thermodynamic potential).For the first time,a tandem structure utilizing organic photoanodes has been computationally designed and fabricated and the implementation of a double PM6:Y6 photoanode/photovoltaic structure resulted in photogenerated currents exceeding 7mA cm^(-2) at 0 VRHE(hydrogen evolution thermodynamic potential)and anodic current onset potentials as low as-0.5 VRHE.The herein-presented organic-based approach paves the way for further exploration of different blend combinations to target specific oxidative reactions by selecting precise donor/acceptor candidates among the multiple existing ones.
基金supported by the National Natural Science Foundation of China(32172010)the Major Program of Guangdong Basic and Applied Basic Research(2019B030302006).
文摘Short tandem repeats(STRs)modulate gene expression and contribute to trait variation.However,a systematic evaluation of the genomic characteristics of STRs has not been conducted,and their influence on gene expression in rice remains unclear.Here,we construct a map of 137,629 polymorphic STRs in the rice(Oryza sativa L.)genome using a population-scale resequencing dataset.A genome-wide survey encompassing 4726 accessions shows that the occurrence frequency,mutational patterns,chromosomal distribution,and functional properties of STRs are correlated with the sequences and lengths of repeat motifs.Leveraging a transcriptome dataset from 127 rice accessions,we identify 44,672 expression STRs(eSTRs)by modeling gene expression in response to the length variation of STRs.These eSTRs are notably enriched in the regulatory regions of genes with active transcriptional signatures.Population analysis identifies numerous STRs that have undergone genetic divergence among different rice groups and 1726 tagged STRs that may be associated with agronomic traits.By editing the(ACT)_(7) STR in OsFD1 promoter,we further experimentally validate its role in regulating gene expression and phenotype.Our study highlights the contribution of STRs to transcriptional regulation in plants and establishes the foundation for their potential use as alternative targets for genetic improvement.
基金supports by the National Natural Science Foundation of China(No.22174037)the Joint Funds of the Hunan Provincial Natural Science Foundation of China(No.2023JJ50255)+1 种基金Changsha Science and Technology Project(No.Z202269490128)National Key Research and Development Program of China(No.2023YFF0613400)are appreciated.
文摘Traditional electrospray ionization tandem mass spectrometry(ESI-MS^(n))has been a powerful tool in diverse research areas,however,it faces great limitations in the study of protein-small molecule interactions.In this article,the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry(TC-ESI-MS^(n))is applied to investigate interactions between ubiquitin and two flavonol molecules,respectively.The combination of collision-induced dissociation(CID)and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges.While structural changes of proteins disturbed by small molecules are unseen in ESI-MS^(n),TC-ESI-MS^(n)allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions,meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data,and the characteristics of structural intermediates.
基金funding support from the National Key Research and Development Program of China(Grant No.2020YFB0408002)the Beijing Natural Science Foundation(Z240024)+2 种基金the National Natural Science Foundation of China(Grant Nos.22279083,22461160281,W2412076)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2022B1515120006)the Central Guiding Local Science and Technology Development Special Fund Project(Grant No.ZYYD2024JD24)。
文摘Tandem solar cells(TSCs)represent an attractive technology that can overcome the single-junction Shockdey-Queisser limit.Recently,a tandem structure combining wide-bandgap metal halide perovskite with complementary bandgap copper indium gallium selenide(CIGS)photovoltaic technology has demonstrated a realistic pathway to achieve the industrialization goal of pushing power conversion efficiency(PCE)approaching 30% at low-cost.In this review,we first pinpoint the unique advantage of perovskite/CIGS tandems with respect to the other mainstream photovoltaic technologies and retrospect the research progress of perovskite/CIGS TSCs from both PCE and stability perspective in the last years.Next,we comprehensively discuss the major advancements in absorbers,functional layers of the individual sub-cell,and the interconnection layer between them in the recent decade.Finally,we outline several essential scientific and engineering challenges that are to be solved toward the development of efficient,long-term stable,and large-area perovskite/CIGS TSCs in the future.
基金National Key Research and Development Program of China (2022YFB420030)National Natural Science Foundation of China (2227903)+1 种基金Innovation Project of Optics Valley Laboratory (OVL2021BG008)Foundation of State Key Laboratory of New Textile Materials and Advanced Processing Technologies (FZ2021011)。
文摘All-perovskite tandem solar cells have the potential to surpass the theoretical efficiency limit of single junction solar cells by reducing thermalization losses.However,the challenges encompass the oxidation of Sn^(2+)to Sn^(4+)and uncontrolled crystallization kinetics in Sn-Pb perovskites,leading to nonradiative recombination and compositional heterogeneity to decrease photovoltaic efficiency and operational stability.Herein,we introduced an ionic liquid additive,1-ethyl-3-methylimidazolium iodide (EMIMI) into Sn-Pb perovskite precursor to form low-dimensional Sn-rich/pure-Sn perovskites at grain boundaries,which mitigates oxidation of Sn^(2+)to Sn^(4+)and regulates the film-forming dynamics of Sn/Pb-based perovskite films.The optimized single-junction Sn-Pb perovskite devices incorporating EMIMI achieved a high efficiency of 22.87%.Furthermore,combined with wide-bandgap perovskite sub-cells in tandem device,we demonstrate 2-terminal all-perovskite tandem solar cells with a power conversion efficiency of 28.34%,achieving improved operational stability.
基金supported by the National Natu-ral Science Foundation of China(Nos.52225204,52173233,and 52202085)the Innovation Program of Shanghai Municipal Edu-cation Commission(No.2021-01-07-00-03-E00109)+4 种基金Natural Sci-ence Foundation of Shanghai(No.23ZR1479200)the Shanghai Sci-entific and Technological Innovation Project(No.24520712800)“Shuguang Program”Supported by the Shanghai Education Devel-opment Foundation and Shanghai Municipal Education Commis-sion(No.20SG33)the Fundamental Research Funds for the Central Universities(No.2232024Y-01)the DHU Distinguished Young Professor Program(Nos.LZA2022001and LZB2023002).
文摘Mesoporous framework supported metal nanoparticle catalyst represents a promising material platform for creating multiple active sites that drive tandem reactions. In this study, we demonstrate a novel catalyst design that involves the encapsulation of CuNi alloy nanoparticles within mesoporous silicon carbide nanofibers (mSiC_(f)) to achieve efficient tandem conversion of furfural (FFA) into 2-(isopropoxymethyl)furan (IPF). The unique one-dimensional (1D) mesoporous structure of mSiC_(f), coupled with abundant oxygen-containing groups, offers a favorable surface microenvironment for the stabilization of bimetallic CuNi active sites. Through carefully optimizing metal to acid sites, we have developed a catalyst containing a total mass ratio of 20 % Cu and Ni, which exhibits a remarkable performance with complete FFA conversion and 92 % IPF selectivity in 4 h. In-depth mechanistic investigations have revealed that the superior activity of this catalyst is attributed to a tandem reaction mechanism. Initially, FFA is hydrogenated at the dual metal active sites to produce furfuryl alcohol (FOL) as an intermediate, which is subsequently etherified at the acid sites with suitable species and strengths on the mSiC_(f) supports. Additionally, the robust 1D mSiC_(f) framework effectively protects the metal sites from agglomeration, resulting in excellent reusability of the catalyst. This study underscores the potential of mesoporous silicon carbide-supported bimetallic active sites for achieving enhanced tandem catalytic functionality.
基金funded by the National Natural Science Foundation of China(Grant Nos.52205457 and 52422511)the National Key R&D Program of China(Grant No.2022YFB4701000)+3 种基金the Guangdong Basic and Applied Basic Research Foundation,China(Grant Nos.2024A1515010043,2025A1515010890 and 2022B1515120011)the Young Talent Support Project of Guangzhou Association for Science and Technology(Grant No.QT2024-010)the Guangzhou Basic and Applied Basic Research Foundation(Grant No.SL2024A04J01501)the State Key Laboratory of Precision Electronic Manufacturing Technology and Equipment(Grant No.JMDZ202303).
文摘The development of high-voltage tandem thin-film supercapacitors(TFSCs)has been limited by the issues such as expensive electrode materials,indispensable commercial separators and metal current collectors,and complex manufacturing processes.Herein,we develop a potentially scalable approach to address all these issues by using CO_(2) laser pyrolysis of polyimide(PI)paper into the three-dimensional(3D)morphology of graphene paper in air.The formation process and mechanism of PI to graphene were clarified by microstructure and chemical characterizations and reaction molecular dynamics.The influences of laser scan density,power,defocus,and scan speed on the sheet resistance,longitudinal resistance,Raman spectra,and electrochemical performance of graphene papers were systematically investigated.Results indicate that high-quality graphene papers with ultralow sheet resistance(4.88Ω·square^(-1))and longitudinal resistance(3.46Ω)and extra-large crystalline size(96.1 nm)were achieved under optimized process parameters.The graphene papers can simultaneously serve as active electrode materials,current collectors,and interconnectors.The active area of electrodes is defined by a PI mask,with the help of which a hydrogel electrolyte functions as a separator.The assembled graphene paper-based TFSCs demonstrate outstanding electrochemical performance and mechanical flexibility,with the areal capacitance of 54.5 mF·cm^(-2),energy density of 10.9µWh·cm^(-2),and cycle stability retention of 86.9%over 15000 cycles.Moreover,all the tandem metal-free TFSCs,ranging from 1 to 160 cells,show excellent performance uniformity.The output voltage increases linearly from 1.2 V to 200 V.Significantly,the 160-tandem TFSCs exhibit a high voltage density within a compact volume of∼3.8 cm^(3).This work provides an avenue for achieving tandem metal-free TFSCs in a simple and efficient manner.
