The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for ...The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.展开更多
Fe-containing graphitic carbon nitride（Fe-g-C3N4） materials were synthesized via one-step pyroly-sis of FeCl3 and dicyandiamide. The physicochemical properties of the synthesized Fe-g-C3N4 sam-ples were characterize...Fe-containing graphitic carbon nitride（Fe-g-C3N4） materials were synthesized via one-step pyroly-sis of FeCl3 and dicyandiamide. The physicochemical properties of the synthesized Fe-g-C3N4 sam-ples were characterized by N2 adsorption-desorption, X-ray diffraction, thermal gravimetric, Fourier transform infrared, UV-vis diffuse reflectance, X-ray photoelectron spectroscopy, and transmission electron microscopy. The Fe cations were anchored by nitrogen-rich g-C3N4, whereas the graphitic structures of g-C3N4 were retained after the introduction of Fe. As heterogeneous catalysts, Fe-g-C3 N4 exhibited good catalytic activity in the direct hydroxylation of benzene to phenol with H2O2, affording a maximum yield of phenol of up to 17.5%. Compared with other Fe- and V-containing g-C3N4 materials, Fe-g-C3N4 features a more convenient preparation procedure and higher catalytic productivity of phenol.展开更多
For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(...For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(MMMs)incorporated by graphene oxide(GO),in which the interlayer channels were regulated to optimize the CO_(2)/N_(2) separation performance.Various membrane preparation conditions were systematically investigated on the influence of the membrane structure and separation performance,including the lateral size of GO nanosheets,GO loading,thermal reduction temperature,and time.The results demonstrated that the precisely regulated interlayer channel of GO nanosheets can rapidly provide CO_(2)-selective transport channels due to the synergetic effects of size sieving and preferential adsorption.The GO/Pebax ultra-thin MMMs exhibited CO_(2)/N_(2) selectivity of 72 and CO_(2) permeance of 400 GPU(1 GPU=106 cm^(3)(STP)·cm^(2)·s^(-1)·cmHg^(-1)),providing a promising candidate for CO_(2) capture.展开更多
The conventional distillation is hard to accomplish the separation of acetonitrile/ethyl acetate/n-hexane mixture. Herein, a heterogeneous azeotropic distillation(HAD) without adding entrainer is proposed to separate ...The conventional distillation is hard to accomplish the separation of acetonitrile/ethyl acetate/n-hexane mixture. Herein, a heterogeneous azeotropic distillation(HAD) without adding entrainer is proposed to separate ternary mixture. The proposed scheme is optimized via the simulated annealing algorithm and minimum total annual cost(TAC) is used as objective functions. To minimize energy consumption,heat pump is added on the basis of optimal heterogeneous azeotropic distillation and heat integration technology is used to further improve the energy recovery. The TAC, gas emission, energy consumption and exergy destruction are used to discuss the economy and environmental protection of processes.Among all the processes, the heat pump with higher preheating temperature(HPT) assisted HAD process by combining with heat integration(HAD-HPT-HI) has best performances on economic, environment,energy and exergy. Compared with conventional HAD process, the HAD-HPT-HI achieves the reductions of 52.17%, 68.86%, 65.87% and 65.46% on TAC, total energy consumption, gas emissions and exergy destruction, respectively.展开更多
Extractive distillation(ED)and solvent-assisted pressure-swing distillation(SA-PSD)are both special distillation processes that perform good at separating pressure-insensitive azeotropes.However,few reported studies h...Extractive distillation(ED)and solvent-assisted pressure-swing distillation(SA-PSD)are both special distillation processes that perform good at separating pressure-insensitive azeotropes.However,few reported studies have compared the performance of the two processes.In this paper,ED processes with N-methylpyrrolidone(NMP)and dimethlac-etamide(DMCA)as entrainer,SA-PSD process with isopropyl-alcohol(IPA)as solvent and SA-PSD process with partial heat integration(PHI-PSD)are proposed to achieve high purity separation of a mixture of cyclohexane/2-butanol system.The optimal operating conditions of the processes are obtained after optimizing with NSGA-Ⅱ algorithm when total annual cost(TAC)and the entropy production of process are set as objectives.The optimal results show that the optimal PHI-PSD process has lower TAC by 28.7% and the lower entropy production by 39.5% than the optimal SA-PSD process while the ED process with NMP as entrainer has lower TAC by 50.9% and the lower entropy production by 56.1% than the optimal SA-PSD process.The optimal results show that the ED process with NMP as entrainer has the best economic and thermodynamic efficiency among the four proposed processes in this paper.展开更多
To improve oil quality,ZSM-22/SAPO-11 composite molecular sieves were synthesized by adding ZSM-22 into a synthetic gel of SAPO-11 for n-decane hydroisomerization.The mass ratios of ZSM-22/(ZSM-22+SAPO-11)in the compo...To improve oil quality,ZSM-22/SAPO-11 composite molecular sieves were synthesized by adding ZSM-22 into a synthetic gel of SAPO-11 for n-decane hydroisomerization.The mass ratios of ZSM-22/(ZSM-22+SAPO-11)in the composite molecular sieves were optimized and the optimal ZSM-22/SAPO-11 composite(ZS-9)was obtained.The electrostatic repulsions between the ZSM-22 precursors and the SAPO-11 crystalline nuclei produced small ZSM-22 and SAPO-11 crystallites in ZS-9,which increased the specific surface area and mesopore volume and thereby exposed more acid sites.In comparison with conventional SAPO-11,ZSM-22 and their mechanical mixture,ZS-9 with smaller crystallites and the optimal medium and strong Brønsted acid centers(MSBAC)content displayed a higher yield of branched C_(10) isomers(81.6%),lower cracking selectivity(11.9%)and excellent stability.The correlation between the i-C_(10) selectivity and the MSBAC density of molecular sieves indicated that the selectivity for branched C_(10) isomers first increased and then decreased with increasing MSBAC density on the molecular sieves,and the maximum selectivity(87.7%)occurred with a density of 9.6×10^(−2)μmol m^(−2).展开更多
With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a h...With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithiumion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Fu rthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in performance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mechanism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to100℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utilization of effective electrode materials and electrolyte components.Furthermore,the safety concerns associated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.展开更多
Electrocatalysis is a surface-sensitive process,in which the catalytic activity of electrocatalyst highly re-lates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the cat-alyt...Electrocatalysis is a surface-sensitive process,in which the catalytic activity of electrocatalyst highly re-lates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the cat-alytically active sites.Surface chemical microenvironment engineering via organic molecules functional-ization is a promising strategy to tune the electrocatalytic activity since it can well modify the elec-trode/electrolyte interface and alter the reaction pathways.In this review,we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules func-tionalization,with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect.More importantly,the applications of organic molecule functionalized catalysts in var-ious electrocatalytic reactions are also systematically summarized,along with a deep discussion on the conclusion and perspective.This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.展开更多
One of the urgent and challenging topics in diversified sustainable energy conversion is the development of high-performance,low-cost,and well durable catalysts.Cu single-atom catalysts(SACs)have become promising cata...One of the urgent and challenging topics in diversified sustainable energy conversion is the development of high-performance,low-cost,and well durable catalysts.Cu single-atom catalysts(SACs)have become promising catalysts for diversified sustainable energy conversion due to their capability to maximize the utilization efficiency,acquire modulated electronic structure and optimized binding strength with intermediates.In this review,we have provided an interview of the recent progress achieved in the field of electrocatalysis,photocatalysis,and heterogeneous reaction based on Cu SACs.Started by this review,we have summarized some advanced synthetic strategies for the construction of Cu SACs.Subsequently,the performance-improving strategies are discussed in terms of the coordination environments of the reaction center,reaction mechanism and selectivity,based on free energy diagram and electron structure analysis.Finally,the remaining issues,challenges,and opportunities of Cu SACs are also provided,affording a perspective for future studies.This review not only offers us a deep understanding on the catalytic mechanism of Cu SACs for energy conversion,but also encourages more endeavors in prompting their practical application.展开更多
Developing dynamic color-tunable ultra-long room temperature phosphorescence(URTP)polymers with afterglow of over 1 s,photo-chromism,and multi-stimuli response for practical anti-counterfeiting and information securit...Developing dynamic color-tunable ultra-long room temperature phosphorescence(URTP)polymers with afterglow of over 1 s,photo-chromism,and multi-stimuli response for practical anti-counterfeiting and information security applications is attractive but very challenging.Herein,by doping multicolor phosphorescence pyri-dinium bromide L block or viologen-based photo-chromic V block into polyvinyl alcohol matrixes,the water-stimuli-responsive color-tunable URTP polymerfilms with afterglow of up to 8 s and the reversible viologen-based photochromic polymerfilms have been developed.More significantly,a series of dynamic color-tunable URTP polymerfilms with ultra-long afterglow of over 6 s,photo-chromism,and water-stimuli response have been successfully exploited by integrating L and V blocks into one polymer system.Mechanistic investigations have revealed that their photo-chromism mainly comes from the photo-generated viologen free radicals.Furthermore,their dynamic multilevel anti-counterfeiting applications have been demonstrated.These results pave the way to develop smarter multifunctional URTP materials for anti-counterfeiting and optical sensing.展开更多
Hierarchical SAPO-11 molecular sieve(ACS-11) was successfully synthesized employing the Al2O3/carbon(Al_(2)O_(3)/C) composite obtained through the pyrolysis of Al-based metal-organic framework(Al-MOF-96)as mesoporogen...Hierarchical SAPO-11 molecular sieve(ACS-11) was successfully synthesized employing the Al2O3/carbon(Al_(2)O_(3)/C) composite obtained through the pyrolysis of Al-based metal-organic framework(Al-MOF-96)as mesoporogen.Unlike other carbon-based mesoporogens with strong hydrophobicity,the Al_(2)O_(3)/C interacts with phosphoric acid and generates the AlPO_(4)/C structure,which promotes the Al2O3/C dispersion in the synthesis gel of SAPO-11 and avoids the phase separation between them.The Al_(2)O_(3)/C as mesoporogen decreases the crystallite size of SAPO-11 via preventing the aggregation of SAPO-11crystals.Additionally,the addition of Al_(2)O_(3)/C improves the Si distribution in the ACS-11 framework.Consequently,ACS-11 has smaller crystallites,more mesopores,and a greater amount of medium Bronsted acid centers than the conventional microporous SAPO-11 and the SAPO-11 synthesized using activated carbon as mesoporogen.The corresponding Pt/ACS-11 catalyst exhibits the maximal selectivity to multi-branched C10isomers(23.28%) and the minimal cracking selectivity(15.83%) in n-decane hydroisomerization among these catalysts.This research provides a new approach for preparing hierarchical silicoaluminophosphate molecular sieve-based catalysts to produce high-quality fuels.展开更多
Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and on...Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and one-electron water oxidation and surface reconstruction derived from the high-oxidative environment co-existed,leading to great challenges to identify the real active sites on the electrode.In this work,Ti/TiO_(2)-based electrodes calcined under air,nitrogen,or urea atmospheres were selected as electrocatalysts for two-electron water oxidation.Electrochemical analyses were applied to evaluate the catalytic activity and selectivity.The morphological and current change on the electrode surface were determined by scanning electrochemical microscopy,while the chemical and valence evolutions with depth distributions were tested by XPS combined with cluster argon ion sputtering.The results demonstrated that Ti/TiO_(2) nanotube arrays served as the support,while the functional groups of carbonyl groups and pyrrolic nitrogen derived from the co-pyrolysis with urea were the active sites for the H_(2)O_(2) production.This finding provided a new horizon to design efficient catalysts for H_(2)O_(2) production.展开更多
Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformati...Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.展开更多
By performing with density functional theory(DFT) method, the detailed adsorption process and the catalytic decarbonylation mechanisms of furfural over Pd(111) and M/Pd(111)(M = Ni, Cu, Ru) surfaces toward furan were ...By performing with density functional theory(DFT) method, the detailed adsorption process and the catalytic decarbonylation mechanisms of furfural over Pd(111) and M/Pd(111)(M = Ni, Cu, Ru) surfaces toward furan were clarified. The results of atomic size factor, formation energy and d-band center showed that Ru/Pd(111) surface was the most stable and active. The adsorption energies of furfural on the different surfaces followed the order Ru/Pd(111) > Cu/Pd(111) > Pd(111) > Ni/Pd(111). After analyzing Mulliken atomic charge population and the deformation density, we can find that on Ru/Pd(111) surface, the number of charge transfer was the most and the interaction was the strongest. Therefore, its adsorption energy was the highest. Furthermore, the furfural decarbonylation pathway is more kinetically feasible on bimetallic surface, and the reaction is the most likely to occur on Ru/Pd(111).展开更多
Abnormal melting point depression of metal nanoparticles often occurs in heterogeneous catalytic reactions,which leads to a reduction in the stability of reactive nanoclusters.To study this abnormal phenomenon,the ori...Abnormal melting point depression of metal nanoparticles often occurs in heterogeneous catalytic reactions,which leads to a reduction in the stability of reactive nanoclusters.To study this abnormal phenomenon,the original and surface-energy modified Gibbs-Thomson equations were analyzed in this work and further modified by considering the effect of the substrate.The results revealed that the original Gibbs-Thomson equation was not suitable for the particles with radii smaller than 10 nm.Moreover,the performance of the surface-energy modified Gibbs-Thomson equation was improved,and the deviation was reduced to(-350-100)K,although further modification of the equation by considering the interfacial effect was necessary for the small particles(r<5 nm).The new model with the interfacial effect improved the model performance with a deviation of approximately-50 to 20 K,where the interfacial effect can be predicted quantitatively from the thermodynamic properties of the metal and substrate.Additionally,the micro-wetting parameterα_W can be used to qualitatively study the overall impact of the substrate on the melting point depression.展开更多
The development of bifunctional electrocatalysts with high activity and stability for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is crucial for efficient overall water splitting but still challe...The development of bifunctional electrocatalysts with high activity and stability for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is crucial for efficient overall water splitting but still challenging.Herein,we propose a facile and effective polymerization–pyrolysis–selenization(PPS)strategy for in-situ synthesis of N-doped carbon nanosnakes(NCNSs)encapsulated Fe-doped CoSe nanoparticles(NPs)derived from predesigned trimetallic Zn/Fe/Co polyphthalocyanine conjugated polymer networks.Benefiting from the synergistic effect between the regulation of Fe atoms and CoSe NPs as well as the confinement effect of in situ formed porous conductive carbon nanosnakes,the FeCoSe@NCNSs catalyst exhibited the excellent electrocatalytic activity for HER with small overpotentials(142 and 99 mV in 0.5 M H_(2)SO_(4) and 1 M KOH)and OER(320 mV in 1 M KOH)at the current density of 10 mA cm^(-2).Particularly,it also can be used as an efficient bifunctional electrocatalyst with a cell voltage of 1.66 V to achieve a current density of 10 mA cm^(-2) and superior stability for overall water splitting.Density functional theory study reveals that the doping of Fe atoms on Co Se enhanced the splitting and delocalization of metal-d orbitals close Fermi level,and modifies the distribution of Se-p orbitals close Fermi level,which improved the flexibility of electron donor-acceptor system and the hydrogen adsorption free energy change on metal-metal bridge sites in FeCoSe@NCNSs.Additionally,beneficial from the accepting of Fe-Se bridge site,the overpotential of OER which following intramolecular oxygen coupling mechanism is also decreased,thus accelerating the electrocatalytic performance.This work presents a novel strategy to regulate the activity and stability of transition metal selenides and facilitating the rational design of bifunctional electrocatalysts for overall water splitting applications.展开更多
The adsorption process and hydrogenation mechanisms of 2-methylthiophene on the Pt（111） surface have been elucidated using density functional theory（DFT）. The optimal adsorption sites of reactants, intermediates, ...The adsorption process and hydrogenation mechanisms of 2-methylthiophene on the Pt（111） surface have been elucidated using density functional theory（DFT）. The optimal adsorption sites of reactants, intermediates, and products as well as the activation energy and reaction energy of each elementary reactions were investigated. The results turned out that the 2-methylthiophene tilt to the Pt（111） catalyst with the C_1–C_2 double bond at the top site was the most stable. During the hydrogenation process, the heat of reaction almost located at the negative side, so dropping the temperature is good for the occurrence of hydrogenation process. The hydrogenation steps of mechanism take place along C_2→C_3→C_1→C_4→S→C_1 to generate the product of pentane-2-thiol, in which the first step with the highest energy barrier is the rate-determining step.展开更多
Third-order optical nonlinearities of three aryloxy substituted phthalocyanines are measured by femtosecond forward degenerate four-wave mixing technique at 800 nm.Ultrafast optical responses are observed and the magn...Third-order optical nonlinearities of three aryloxy substituted phthalocyanines are measured by femtosecond forward degenerate four-wave mixing technique at 800 nm.Ultrafast optical responses are observed and the magnitude of the second-order hyperpolarizabilitiesγof the phthalocyanines is measured to be as large as 10?31 esu.Due to the enhancement of J-aggregates,theγvalue of an aryloxy substituted zinc phthalocyanine in chloroform is approximately 2.2 times larger than that of the dye in methanol.Moreover,the morphologies of aryloxy substituted zinc phthalocyanine in chloroform exhibit that the nanowires with a diameter of 50–100 nm are connected to each other to form an indefinite network structure,while no aggregates are detected when the samples are prepared from a solution in the methanol.展开更多
Indonesian oil sands were systematically separated to investigate their basic composition.The extraction effects of the solvents with different Hilderbrand solubility parameters(HSPs)on the bitumen of Indonesian oil s...Indonesian oil sands were systematically separated to investigate their basic composition.The extraction effects of the solvents with different Hilderbrand solubility parameters(HSPs)on the bitumen of Indonesian oil sands were compared.Furthermore,the Hansen solubility combination parameter(HSCP)and Teas triangle were used to explore rules in the separation of oil sands bitumen via solvent extraction.Finally,the saturates,aromatics,resins,and asphaltenes(SARA)fractions of the bitumen from Indonesian oil sands were analyzed.The results showed that the Indonesian oil sands were oil-wet with a bitumen content of 24.93%.The solvent extraction for bitumen could be accurately and conveniently selected based on the solubility parameter.When the HSPs of the extraction solvent were around 18–19 and the HSCPs were closer to a certain range(δ_(d)=17.5–18.0,δ_(p)=1–3.5,and δ_(h)=2–6),the extraction effect of bitumen from Indonesian oil sands improved,and the primary component affecting the extraction rate of bitumen were asphaltenes.展开更多
Improving catalytic activity and durabilty through the structural and compositional development of bifunctional electrocatalysts with low cost,high activity and stability is a challenging issue in electrochemical wate...Improving catalytic activity and durabilty through the structural and compositional development of bifunctional electrocatalysts with low cost,high activity and stability is a challenging issue in electrochemical water splitting.Herein,we report the fabrication of heterostructured P-CoMoO_(4)@NiCoP on a Ni foam substrate through interface engineering,by adjusting its composition and architecture.Benefitting from the tailored electronic structure and exposed active sites,the heterostructured P-CoMoO_(4)@NiCoP/NF arrays can be coordinated to boost the overall water splitting.In addition,the superhydrophilic and superaerophobic properties of P-CoMoO_(4)@NiCoP/NF make it conducive to water dissociation and bubble separation in the electrocatalytic process.The heterostructured PCoMoO_(4)@NiCoP/NF exhibits excellent bifunctional electrocatalysis activity with a low overpotential of 66 mV at 10 mA cm^(-2) for HER and 252 mV at 100 mA cm^(-2) for OER.Only 1.62 V potential is required to deliver 20 mA cm^(-2) in a two-electrode electrolysis system,providing a decent overall water splitting performance.The rational construction of the heterostructure makes it possible to regulate the electronic structures and active sites of the electrocatalysts to promote their catalytic activity.展开更多
基金supported by the National Natural Science Foundation of China(22108238,21878259)the Zhejiang Provincial Natural Science Foundation of China(LR18B060001)+5 种基金Anhui Provincial Natural Science Founda-tion(1908085QB68)the Natural Science Foundation of the Anhui Higher Education Institutions of China(KJ2020A0275)Major Science and Technology Project of Anhui Province(201903a05020055)Foundation of Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology(ZJKL-ACEMT-1802)China Postdoctoral Science Foundation(2019M662060,2020T130580)Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(BM2012110).
文摘The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.
基金supported by the National Natural Science Foundation of China (21673024)Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (ACGM2016-06-28)+1 种基金Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2017-K28)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (PPZY2015B145)~~
文摘Fe-containing graphitic carbon nitride（Fe-g-C3N4） materials were synthesized via one-step pyroly-sis of FeCl3 and dicyandiamide. The physicochemical properties of the synthesized Fe-g-C3N4 sam-ples were characterized by N2 adsorption-desorption, X-ray diffraction, thermal gravimetric, Fourier transform infrared, UV-vis diffuse reflectance, X-ray photoelectron spectroscopy, and transmission electron microscopy. The Fe cations were anchored by nitrogen-rich g-C3N4, whereas the graphitic structures of g-C3N4 were retained after the introduction of Fe. As heterogeneous catalysts, Fe-g-C3 N4 exhibited good catalytic activity in the direct hydroxylation of benzene to phenol with H2O2, affording a maximum yield of phenol of up to 17.5%. Compared with other Fe- and V-containing g-C3N4 materials, Fe-g-C3N4 features a more convenient preparation procedure and higher catalytic productivity of phenol.
基金financially supported by The Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB530007,22KJA530001)National Natural Science Foundation of China(22208151)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20220002)the State Key Laboratory of MaterialsOriented Chemical Engineering(SKL-MCE-22B07).
文摘For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(MMMs)incorporated by graphene oxide(GO),in which the interlayer channels were regulated to optimize the CO_(2)/N_(2) separation performance.Various membrane preparation conditions were systematically investigated on the influence of the membrane structure and separation performance,including the lateral size of GO nanosheets,GO loading,thermal reduction temperature,and time.The results demonstrated that the precisely regulated interlayer channel of GO nanosheets can rapidly provide CO_(2)-selective transport channels due to the synergetic effects of size sieving and preferential adsorption.The GO/Pebax ultra-thin MMMs exhibited CO_(2)/N_(2) selectivity of 72 and CO_(2) permeance of 400 GPU(1 GPU=106 cm^(3)(STP)·cm^(2)·s^(-1)·cmHg^(-1)),providing a promising candidate for CO_(2) capture.
基金financial support provided by the National Natural Science Foundation of China (22178030, 21878025, and 22078026)。
文摘The conventional distillation is hard to accomplish the separation of acetonitrile/ethyl acetate/n-hexane mixture. Herein, a heterogeneous azeotropic distillation(HAD) without adding entrainer is proposed to separate ternary mixture. The proposed scheme is optimized via the simulated annealing algorithm and minimum total annual cost(TAC) is used as objective functions. To minimize energy consumption,heat pump is added on the basis of optimal heterogeneous azeotropic distillation and heat integration technology is used to further improve the energy recovery. The TAC, gas emission, energy consumption and exergy destruction are used to discuss the economy and environmental protection of processes.Among all the processes, the heat pump with higher preheating temperature(HPT) assisted HAD process by combining with heat integration(HAD-HPT-HI) has best performances on economic, environment,energy and exergy. Compared with conventional HAD process, the HAD-HPT-HI achieves the reductions of 52.17%, 68.86%, 65.87% and 65.46% on TAC, total energy consumption, gas emissions and exergy destruction, respectively.
基金supported by the National Natural Science Foundation of China(22178030,21878025,22078026)。
文摘Extractive distillation(ED)and solvent-assisted pressure-swing distillation(SA-PSD)are both special distillation processes that perform good at separating pressure-insensitive azeotropes.However,few reported studies have compared the performance of the two processes.In this paper,ED processes with N-methylpyrrolidone(NMP)and dimethlac-etamide(DMCA)as entrainer,SA-PSD process with isopropyl-alcohol(IPA)as solvent and SA-PSD process with partial heat integration(PHI-PSD)are proposed to achieve high purity separation of a mixture of cyclohexane/2-butanol system.The optimal operating conditions of the processes are obtained after optimizing with NSGA-Ⅱ algorithm when total annual cost(TAC)and the entropy production of process are set as objectives.The optimal results show that the optimal PHI-PSD process has lower TAC by 28.7% and the lower entropy production by 39.5% than the optimal SA-PSD process while the ED process with NMP as entrainer has lower TAC by 50.9% and the lower entropy production by 56.1% than the optimal SA-PSD process.The optimal results show that the ED process with NMP as entrainer has the best economic and thermodynamic efficiency among the four proposed processes in this paper.
基金The authors gratefully acknowledge the financial support of Science Foundation of China University of Petroleum,Beijing(Grant No.KYJJ2012-03-03).
文摘To improve oil quality,ZSM-22/SAPO-11 composite molecular sieves were synthesized by adding ZSM-22 into a synthetic gel of SAPO-11 for n-decane hydroisomerization.The mass ratios of ZSM-22/(ZSM-22+SAPO-11)in the composite molecular sieves were optimized and the optimal ZSM-22/SAPO-11 composite(ZS-9)was obtained.The electrostatic repulsions between the ZSM-22 precursors and the SAPO-11 crystalline nuclei produced small ZSM-22 and SAPO-11 crystallites in ZS-9,which increased the specific surface area and mesopore volume and thereby exposed more acid sites.In comparison with conventional SAPO-11,ZSM-22 and their mechanical mixture,ZS-9 with smaller crystallites and the optimal medium and strong Brønsted acid centers(MSBAC)content displayed a higher yield of branched C_(10) isomers(81.6%),lower cracking selectivity(11.9%)and excellent stability.The correlation between the i-C_(10) selectivity and the MSBAC density of molecular sieves indicated that the selectivity for branched C_(10) isomers first increased and then decreased with increasing MSBAC density on the molecular sieves,and the maximum selectivity(87.7%)occurred with a density of 9.6×10^(−2)μmol m^(−2).
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20220618)the National Natural Science Foundation of China(Nos.22078028 and 21978026)。
文摘With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithiumion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Fu rthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in performance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mechanism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to100℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utilization of effective electrode materials and electrolyte components.Furthermore,the safety concerns associated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.
基金supported by the Key Research&Development and Promotion Projects in Henan Province(No.232102230079).
文摘Electrocatalysis is a surface-sensitive process,in which the catalytic activity of electrocatalyst highly re-lates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the cat-alytically active sites.Surface chemical microenvironment engineering via organic molecules functional-ization is a promising strategy to tune the electrocatalytic activity since it can well modify the elec-trode/electrolyte interface and alter the reaction pathways.In this review,we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules func-tionalization,with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect.More importantly,the applications of organic molecule functionalized catalysts in var-ious electrocatalytic reactions are also systematically summarized,along with a deep discussion on the conclusion and perspective.This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.
基金financially supported by the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX21_2795)the Basic Science(Natural Science)Research Project of Colleges and Universities of Jiangsu Province(No.21KJB540001)Changzhou Sci&Tech Program(Nos.CJ20220180,CJ20210042),China.
文摘One of the urgent and challenging topics in diversified sustainable energy conversion is the development of high-performance,low-cost,and well durable catalysts.Cu single-atom catalysts(SACs)have become promising catalysts for diversified sustainable energy conversion due to their capability to maximize the utilization efficiency,acquire modulated electronic structure and optimized binding strength with intermediates.In this review,we have provided an interview of the recent progress achieved in the field of electrocatalysis,photocatalysis,and heterogeneous reaction based on Cu SACs.Started by this review,we have summarized some advanced synthetic strategies for the construction of Cu SACs.Subsequently,the performance-improving strategies are discussed in terms of the coordination environments of the reaction center,reaction mechanism and selectivity,based on free energy diagram and electron structure analysis.Finally,the remaining issues,challenges,and opportunities of Cu SACs are also provided,affording a perspective for future studies.This review not only offers us a deep understanding on the catalytic mechanism of Cu SACs for energy conversion,but also encourages more endeavors in prompting their practical application.
基金Priority Academic Program Development of Jiangsu Higher Education InstitutionsApplied Basic Research Programs of Science and Technology Commission Foundation of Jiangsu Province,Grant/Award Number:BK20231340+4 种基金Changzhou Introduction Program of Innovative Leading Talents,Grant/Award Number:CQ20220111Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20170290Natural Science Foundation of the Higher Education Institutions of Jiangsu Province,Grant/Award Number:17KJB150002Opening Project of Zhejiang Engineering Research Center of Fat-soluble Vitamin,Grant/Award Number:202107National Natural Science Foundation of China,Grant/Award Numbers:51803143,。
文摘Developing dynamic color-tunable ultra-long room temperature phosphorescence(URTP)polymers with afterglow of over 1 s,photo-chromism,and multi-stimuli response for practical anti-counterfeiting and information security applications is attractive but very challenging.Herein,by doping multicolor phosphorescence pyri-dinium bromide L block or viologen-based photo-chromic V block into polyvinyl alcohol matrixes,the water-stimuli-responsive color-tunable URTP polymerfilms with afterglow of up to 8 s and the reversible viologen-based photochromic polymerfilms have been developed.More significantly,a series of dynamic color-tunable URTP polymerfilms with ultra-long afterglow of over 6 s,photo-chromism,and water-stimuli response have been successfully exploited by integrating L and V blocks into one polymer system.Mechanistic investigations have revealed that their photo-chromism mainly comes from the photo-generated viologen free radicals.Furthermore,their dynamic multilevel anti-counterfeiting applications have been demonstrated.These results pave the way to develop smarter multifunctional URTP materials for anti-counterfeiting and optical sensing.
基金financial support of Science Foundation of China University of Petroleum,Beijing(Grant No.KYJJ2012-03-03)
文摘Hierarchical SAPO-11 molecular sieve(ACS-11) was successfully synthesized employing the Al2O3/carbon(Al_(2)O_(3)/C) composite obtained through the pyrolysis of Al-based metal-organic framework(Al-MOF-96)as mesoporogen.Unlike other carbon-based mesoporogens with strong hydrophobicity,the Al_(2)O_(3)/C interacts with phosphoric acid and generates the AlPO_(4)/C structure,which promotes the Al2O3/C dispersion in the synthesis gel of SAPO-11 and avoids the phase separation between them.The Al_(2)O_(3)/C as mesoporogen decreases the crystallite size of SAPO-11 via preventing the aggregation of SAPO-11crystals.Additionally,the addition of Al_(2)O_(3)/C improves the Si distribution in the ACS-11 framework.Consequently,ACS-11 has smaller crystallites,more mesopores,and a greater amount of medium Bronsted acid centers than the conventional microporous SAPO-11 and the SAPO-11 synthesized using activated carbon as mesoporogen.The corresponding Pt/ACS-11 catalyst exhibits the maximal selectivity to multi-branched C10isomers(23.28%) and the minimal cracking selectivity(15.83%) in n-decane hydroisomerization among these catalysts.This research provides a new approach for preparing hierarchical silicoaluminophosphate molecular sieve-based catalysts to produce high-quality fuels.
基金Project(2021JJ30792) supported by the Natural Science Foundation of Hunan Province,ChinaProject(52170031) supported by the National Natural Science Foundation of ChinaProject supported by the Fundamental Research Funds for the Central Universities,China。
文摘Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and one-electron water oxidation and surface reconstruction derived from the high-oxidative environment co-existed,leading to great challenges to identify the real active sites on the electrode.In this work,Ti/TiO_(2)-based electrodes calcined under air,nitrogen,or urea atmospheres were selected as electrocatalysts for two-electron water oxidation.Electrochemical analyses were applied to evaluate the catalytic activity and selectivity.The morphological and current change on the electrode surface were determined by scanning electrochemical microscopy,while the chemical and valence evolutions with depth distributions were tested by XPS combined with cluster argon ion sputtering.The results demonstrated that Ti/TiO_(2) nanotube arrays served as the support,while the functional groups of carbonyl groups and pyrrolic nitrogen derived from the co-pyrolysis with urea were the active sites for the H_(2)O_(2) production.This finding provided a new horizon to design efficient catalysts for H_(2)O_(2) production.
文摘Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.
基金supported by the National Natural Science Foundation of China(No.21503188)
文摘By performing with density functional theory(DFT) method, the detailed adsorption process and the catalytic decarbonylation mechanisms of furfural over Pd(111) and M/Pd(111)(M = Ni, Cu, Ru) surfaces toward furan were clarified. The results of atomic size factor, formation energy and d-band center showed that Ru/Pd(111) surface was the most stable and active. The adsorption energies of furfural on the different surfaces followed the order Ru/Pd(111) > Cu/Pd(111) > Pd(111) > Ni/Pd(111). After analyzing Mulliken atomic charge population and the deformation density, we can find that on Ru/Pd(111) surface, the number of charge transfer was the most and the interaction was the strongest. Therefore, its adsorption energy was the highest. Furthermore, the furfural decarbonylation pathway is more kinetically feasible on bimetallic surface, and the reaction is the most likely to occur on Ru/Pd(111).
基金Financial supports from Key Project(21838004)Joint Research Fund for Overseas Chinese,Hong Kong,Macao Young Scientists of National Natural Science Foundation(21729601)of China+1 种基金the Swedish Research Councilthe Kempe Foundation for financial support。
文摘Abnormal melting point depression of metal nanoparticles often occurs in heterogeneous catalytic reactions,which leads to a reduction in the stability of reactive nanoclusters.To study this abnormal phenomenon,the original and surface-energy modified Gibbs-Thomson equations were analyzed in this work and further modified by considering the effect of the substrate.The results revealed that the original Gibbs-Thomson equation was not suitable for the particles with radii smaller than 10 nm.Moreover,the performance of the surface-energy modified Gibbs-Thomson equation was improved,and the deviation was reduced to(-350-100)K,although further modification of the equation by considering the interfacial effect was necessary for the small particles(r<5 nm).The new model with the interfacial effect improved the model performance with a deviation of approximately-50 to 20 K,where the interfacial effect can be predicted quantitatively from the thermodynamic properties of the metal and substrate.Additionally,the micro-wetting parameterα_W can be used to qualitatively study the overall impact of the substrate on the melting point depression.
基金supported by the Taishan Scholars Program of Shandong Province (No. tsqn201909065)the National Natural Science Foundation of China (No. 22108306)+3 种基金the Shandong Provincial Natural Science Foundation (ZR2020QB174, ZR2021YQ15)the Postgraduate Innovation Fund of China University of Petroleum(East China)(No. YCX2020037)the State Key Laboratory of Organic-Inorganic Composites (oic-202101006)the Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University),Ministry of Education。
文摘The development of bifunctional electrocatalysts with high activity and stability for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is crucial for efficient overall water splitting but still challenging.Herein,we propose a facile and effective polymerization–pyrolysis–selenization(PPS)strategy for in-situ synthesis of N-doped carbon nanosnakes(NCNSs)encapsulated Fe-doped CoSe nanoparticles(NPs)derived from predesigned trimetallic Zn/Fe/Co polyphthalocyanine conjugated polymer networks.Benefiting from the synergistic effect between the regulation of Fe atoms and CoSe NPs as well as the confinement effect of in situ formed porous conductive carbon nanosnakes,the FeCoSe@NCNSs catalyst exhibited the excellent electrocatalytic activity for HER with small overpotentials(142 and 99 mV in 0.5 M H_(2)SO_(4) and 1 M KOH)and OER(320 mV in 1 M KOH)at the current density of 10 mA cm^(-2).Particularly,it also can be used as an efficient bifunctional electrocatalyst with a cell voltage of 1.66 V to achieve a current density of 10 mA cm^(-2) and superior stability for overall water splitting.Density functional theory study reveals that the doping of Fe atoms on Co Se enhanced the splitting and delocalization of metal-d orbitals close Fermi level,and modifies the distribution of Se-p orbitals close Fermi level,which improved the flexibility of electron donor-acceptor system and the hydrogen adsorption free energy change on metal-metal bridge sites in FeCoSe@NCNSs.Additionally,beneficial from the accepting of Fe-Se bridge site,the overpotential of OER which following intramolecular oxygen coupling mechanism is also decreased,thus accelerating the electrocatalytic performance.This work presents a novel strategy to regulate the activity and stability of transition metal selenides and facilitating the rational design of bifunctional electrocatalysts for overall water splitting applications.
基金supported by the Special Program for Key Basic Research of the Ministry of Science and Technology,China(No.2014CB460608)
文摘The adsorption process and hydrogenation mechanisms of 2-methylthiophene on the Pt（111） surface have been elucidated using density functional theory（DFT）. The optimal adsorption sites of reactants, intermediates, and products as well as the activation energy and reaction energy of each elementary reactions were investigated. The results turned out that the 2-methylthiophene tilt to the Pt（111） catalyst with the C_1–C_2 double bond at the top site was the most stable. During the hydrogenation process, the heat of reaction almost located at the negative side, so dropping the temperature is good for the occurrence of hydrogenation process. The hydrogenation steps of mechanism take place along C_2→C_3→C_1→C_4→S→C_1 to generate the product of pentane-2-thiol, in which the first step with the highest energy barrier is the rate-determining step.
基金Supported by the National Natural Science Foundation of China under Grant No 2077307Program for Advantage Discipline of Changzhou University,Research Foundation for Talented Scholars of Changzhou University under Grant No ZMF11020007+1 种基金Project for Six Major Talent Peaks of Jiangsu Province under Grant No 2011-XCL-004the Natural Science Foundation of Changzhou City under Grant No CJ20115009.
文摘Third-order optical nonlinearities of three aryloxy substituted phthalocyanines are measured by femtosecond forward degenerate four-wave mixing technique at 800 nm.Ultrafast optical responses are observed and the magnitude of the second-order hyperpolarizabilitiesγof the phthalocyanines is measured to be as large as 10?31 esu.Due to the enhancement of J-aggregates,theγvalue of an aryloxy substituted zinc phthalocyanine in chloroform is approximately 2.2 times larger than that of the dye in methanol.Moreover,the morphologies of aryloxy substituted zinc phthalocyanine in chloroform exhibit that the nanowires with a diameter of 50–100 nm are connected to each other to form an indefinite network structure,while no aggregates are detected when the samples are prepared from a solution in the methanol.
基金supported by the Natural Science Foundation of Jiangsu Province(Grant number:BK20140260)Joint Project of Industry-University-Research of Jiangsu Province(Grant number:BY2018158,BY2021590)State Key Laboratory of Heavy Oil Processing.
文摘Indonesian oil sands were systematically separated to investigate their basic composition.The extraction effects of the solvents with different Hilderbrand solubility parameters(HSPs)on the bitumen of Indonesian oil sands were compared.Furthermore,the Hansen solubility combination parameter(HSCP)and Teas triangle were used to explore rules in the separation of oil sands bitumen via solvent extraction.Finally,the saturates,aromatics,resins,and asphaltenes(SARA)fractions of the bitumen from Indonesian oil sands were analyzed.The results showed that the Indonesian oil sands were oil-wet with a bitumen content of 24.93%.The solvent extraction for bitumen could be accurately and conveniently selected based on the solubility parameter.When the HSPs of the extraction solvent were around 18–19 and the HSCPs were closer to a certain range(δ_(d)=17.5–18.0,δ_(p)=1–3.5,and δ_(h)=2–6),the extraction effect of bitumen from Indonesian oil sands improved,and the primary component affecting the extraction rate of bitumen were asphaltenes.
基金The authors acknowledge the National Natural Science Foundation of China(NSFC 91834301,21808046 and 21908037)Anhui Provincial Science and Technology Department Foundation(201903a05020021 and 202003a05020046)for funding support.
文摘Improving catalytic activity and durabilty through the structural and compositional development of bifunctional electrocatalysts with low cost,high activity and stability is a challenging issue in electrochemical water splitting.Herein,we report the fabrication of heterostructured P-CoMoO_(4)@NiCoP on a Ni foam substrate through interface engineering,by adjusting its composition and architecture.Benefitting from the tailored electronic structure and exposed active sites,the heterostructured P-CoMoO_(4)@NiCoP/NF arrays can be coordinated to boost the overall water splitting.In addition,the superhydrophilic and superaerophobic properties of P-CoMoO_(4)@NiCoP/NF make it conducive to water dissociation and bubble separation in the electrocatalytic process.The heterostructured PCoMoO_(4)@NiCoP/NF exhibits excellent bifunctional electrocatalysis activity with a low overpotential of 66 mV at 10 mA cm^(-2) for HER and 252 mV at 100 mA cm^(-2) for OER.Only 1.62 V potential is required to deliver 20 mA cm^(-2) in a two-electrode electrolysis system,providing a decent overall water splitting performance.The rational construction of the heterostructure makes it possible to regulate the electronic structures and active sites of the electrocatalysts to promote their catalytic activity.
