Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquiox...Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis</span></span><span style="font-family:Verdana;">(</span><span style="font-family:Verdana;">isobutyronitrile</span><span style="font-family:Verdana;">)</span><span style="font-family:Verdana;"> (AIBN) at 60</span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration </span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">system</span><span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or </span><span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA</span><span style="font-family:Verdana;"> porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. The porous polymer was also obtained </span><span style="font-family:Verdana;">by</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">using</span><span style="font-family:""><span style="font-family:Verdana;"> a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of </span><span style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased</span><span style="font-family:Verdana;"> with </span><span style="font-family:Verdana;">increasing in the monomer concentration </span></span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction systems. Thioliso</span><span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 </span><span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate</span><span style="font-family:Verdana;"> (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and </span><i><span style="font-family:Verdana;">N,N</span></i><span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected </span><span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the</span><span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger </span><span style="font-family:Verdana;">than </span></span><span style="font-family:Verdana;">those</span><span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers</span><span style="font-family:Verdana;"> started at round 260</span><span style="font-family:Verdana;">°</span><span style="font-family:""><span style="font-family:Verdana;">C and showed </span><span style="font-family:Verdana;">endothermic peak at around 350</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C derived from degradation of </span><span style="font-family:Verdana;">thio-urethane bond.展开更多
Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD...Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.展开更多
A series of benzimidazole-linked porous polymers are obtained by the condensation reaction between the o-aminobenzol end groups of building blocks(2,3,6,7,10,11-hexaaminotriphenylene,3,3'-diaminobenzidine or 1,2,4...A series of benzimidazole-linked porous polymers are obtained by the condensation reaction between the o-aminobenzol end groups of building blocks(2,3,6,7,10,11-hexaaminotriphenylene,3,3'-diaminobenzidine or 1,2,4,5-benzenetetraamine)and the aldehyde groups of building blocks[terephthalicaldehyde,4,4'-biphenyl-dicarboxaldehyde,1,3,5-tris(4-acetylphenyl)benzene or 1,3,5-tris(4-formylbiphenyl)amine]in one-pot synthesis without employing any catalyst or template.The existence of the imidazole ring in the obtained polymers could be identified by Fourier transform infrared and solid-state^(13)C CP/MAS NMR spectroscopy.The sphere-shaped mor-phology of the obtained polymers is observed through scanning electron microscopy.The polymers possess Brunauer-Emmett-Teller specific surface area values over 600 m^(2)·g^(-1),showing hydrogen storage(up to 1.6 wt%,at 77 K and 1×10^(5)Pa)and carbon dioxide capture(up to 12.6 wt%,at 273 K and 1×10^(5)Pa)properties.Such poly-mers would possess good performance in the applications of gas storage and separation.展开更多
Micro/nano-porous polymeric material is considered a unique industrial material due to its extremelylow thermal conductivity, low density, and high surface area. Therefore, it is necessary to establishan accurate ther...Micro/nano-porous polymeric material is considered a unique industrial material due to its extremelylow thermal conductivity, low density, and high surface area. Therefore, it is necessary to establishan accurate thermal conductivity prediction model suiting their applicable conditions and provide atheoretical basis for expanding their applications. In this work, the development of the calculationmodel of equivalent thermal conductivity of micro/nano-porous polymeric materials in recent yearsis summarized. Firstly, it reviews the process of establishing the overall equivalent thermal conductivity calculation model for micro/nanoporous polymers. Then, the predicted calculation models ofthermal conductivity are introduced separately according to the conductive and radiative thermalconductivity models. In addition, the thermal conduction part is divided into the gaseous thermalconductivity model, solid thermal conductivity model and gas-solid coupling model. Finally, it isconcluded that, compared with other porous materials, there are few studies on heat transfer of micro/nanoporous polymers, especially on the particular heat transfer mechanisms such as scale effectsat the micro/nanoscale. In particular, the following aspects of porous polymers still need to be furtherstudied: micro scaled thermal radiation, heat transfer characteristics of particular morphologies at thenanoscales, heat transfer mechanism and impact factors of micro/nanoporous polymers. Such studieswould provide a more accurate prediction of thermal conductivity and a broader application in energyconversion and storage systems.展开更多
In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxyme...In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural(EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran(THF). The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H(100) at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers(PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.展开更多
Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with...Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with zero-dimensional spherical shapes.However, owing to the limitations of synthetic methods, construction of porous building blocks in one dimension featuring high aspect ratios for porous nanonetwork structured polymer(PNSP) remains largely unexplored. Here we present the successful design and preparation of PNSP with a novel type of one-dimensional network unit, i.e., microporous heterogeneous nanowire. Well-defined core-shell polymer nanoobjects prepared from a gelable block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene are employed as building blocks, and facilely transformed into PNSP via hypercrosslinking of polystyrene shell. The as-prepared PNSP exhibits unique three-dimensional hierarchical nanonetwork morphologies with large surface area. These findings could provide a new avenue for fabrication of unique well-defined PNSP, and thus generate valuable breakthroughs in many applications.展开更多
A series of thiophene-based conjugated microporous polymers(ThPOPs) have been synthesized on the basis of ferric chloride-catalyzed oxidative coupling polymerization of multi-thienyl monomers. The structures of ThPOPs...A series of thiophene-based conjugated microporous polymers(ThPOPs) have been synthesized on the basis of ferric chloride-catalyzed oxidative coupling polymerization of multi-thienyl monomers. The structures of ThPOPs were confirmed via solid-state 13 C CP/MAS NMR spectroscopy and Fourier-transform infrared spectroscopy. The ThPOPs possess high porosities and their high Brunauer-Emmett-Teller specific surface area results vary between 350 and 1320 m^2 g^(-1). The presence of abundant ultra-micropores at 0.50–0.63 nm allows ThPOPs efficient gas(carbon dioxide, methane, and hydrogen) adsorption.展开更多
Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from ...Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.展开更多
The widespread use of bisphenol A(BPA)poses a serious threat to the environment and human health.However,efficient removal of BPA in water is incredibly challenging,owing to the inert chemical nature and electrical ne...The widespread use of bisphenol A(BPA)poses a serious threat to the environment and human health.However,efficient removal of BPA in water is incredibly challenging,owing to the inert chemical nature and electrical neutrality of BPA.In order to solve this problem,for the first time,we propose that a strategy of designing conjugated porous polymers with the pore size matching the size of BPA can greatly enhance the binding force of BPA.On this basis,we developed a novel conjugated poly 1,3,5-tri[4-(diphenylamino)phenyl]benzene(MPDPB)with intrinsic pore matching the size of BPA and multi-stage porous structure by editing polymerization with nitrobenzene.The binding energy of MPDPB to BPA is the highest at present(37.84 kcal/mol),which is 2.3 times that of the most powerful adsorbent previously reported and five times that of the conventional adsorbent.These advantages make MPDPB have super-high adsorption performance towards BPA and high absorbing stability under extreme environments.Impressively,MPDPB could be easily loaded on a non-woven fabric to generate point-of-use devices,which could eliminate more than 99.8%of BPA,making it the best BPA candidate adsorbent material.We believe that the proposed material design derived from the specific structure of the contaminant molecule can be extended to exploring further innovative adsorbents.展开更多
Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO_(2)) capture. However, the regeneration of the CO_(2) still faces the problem of high energy cost. Here we synthe...Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO_(2)) capture. However, the regeneration of the CO_(2) still faces the problem of high energy cost. Here we synthesize a near-infrared region(NIR) light responsive conjugated porous polymer(PDPP-Gu) [DPP=3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] by constructing porous amorphous networks with a side chain engineering strategy to regulate CO_(2) adsorption and release through photothermal conversion. The PDPP-Gu is featured by a torsional conjugated backbone as well as a functional side chain of guanidino group. The donor-acceptor configuration of PDPP-Gu afforded strong absorption in the NIR and an excellent photothermal conversion capability of up to 48.8%, as well as a high surface energy. Moreover, guanidine modified side chain further enhanced the CO_(2)-polymers interactions, resulting in a high CO_(2) selective adsorption capacity(0.8 mmol/g) at 273 K, 1 bar(1 bar=105 Pa). The adsorbed CO_(2) can be released under NIR light irradiation. This strategy of molecule design combined the dual features of photothermal conversion and gas adsorption, which is beneficial for the development of materials to dynamically control the adsorption and release of CO_(2) through NIR light.展开更多
Nitrogen-rich porous organic polymers have shown great potentials in gas adsorption/separation,photocatalysis,electrochemistry,sensing and so on.Herein,1,2,3-triazole functionalized triazine-based porous organic polym...Nitrogen-rich porous organic polymers have shown great potentials in gas adsorption/separation,photocatalysis,electrochemistry,sensing and so on.Herein,1,2,3-triazole functionalized triazine-based porous organic polymers(TT-POPs)have been synthesized by the copper-catalyzed azide-alkyne cycloaddition(Cu-AAC)polymerization reactions of 1,3,5-tris(4-azidophenyl)-triazine with 1,4-diacetylene benzene and 1,3,5-triacetylenebenzene,respectively.The characterizations of N2 adsorption at 77 K show TTPOPs possess permanent porosity with BET surface areas of 666 m^(2)·g^(-1)(TT-POP-1)and 406 m^(2)·g^(-1)(TT-POP-2).The adsorption capacities of TT-POPs for CO_(2),CH4,C2H2 and C2H4,as well as the selective separation abilities of CO_(2)/N2,CO_(2)/CH_(4),C_(2)H_(2)/CH_(4) and C_(2)H_(4)/CH_(4) were evaluated.The gas selective separation ratio of TT-POPs was calculated by the ideal adsorbed solution theory(IAST)method,wherein the selective separation ratios of C_(2)H_(2)/CH_(4) and C_(2)H_(4)/CH_(4) of TT-POP-2 was 48.4 and 13.6(298 K,0.1 MPa),which is comparable to other adsorbents(5.6–120.6 for C_(2)H_(2)/CH_(4),10–26 for C_(2)H_(4)/CH_(4)).This work shows that the 1,2,3-triazole functionalized triazine-based porous organic polymer has a good application prospect in natural gas purification.展开更多
Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct metho...Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct method for obtaining the high flux is to decrease membrane thickness.Polyamide(PA)nanofiltration membrane is conventionally prepared by the direct interfacial polymerization(IP)on substrate surface,and results in a thick PA layer.In this work,we proposed a strategy that constructing triazine-based porous organic polymer(TRZ-POP)as the interlayer to prepare the ultrathin PA nanofiltration membranes.TRZ-POP is firstly deposited on the polyethersulfone substrate,and then the formed TRZ-POP provides more adhesion sites towards PA based on its high specific surface areas.The chemical bonding between terminal amine group of TRZ-POP and the amide group of PA further improves the binding force,and strengthens the stability of PA layer.More importantly,the high porosity of TRZPOP layer causes the higher polymerization of initial PA owning to the stored sufficient amino monomer;and H-bonding interaction between amine groups of TRZ-POP and piperazine(PIP)can astrict the release of PIP.Thus,IP process is controlled,and the thinnest thickness of prepared PA layer is only<15 nm.As expected,PA/TRZ-POP membrane shows a more excellent water flux of 1414 L·m^(-2)·h^(-1)·MPa^(-1)than that of the state-of-the-art nanofiltration membranes,and without sacrificing dye rejection.The build of TRZPOP interlayer develops a new method for obtaining a high-flux nanofiltration membrane.展开更多
Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to p...Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.展开更多
Nitrogen-rich porous organic polymers(POPs)with basic features have already shown promising performance in various organic reactions.But the harsh conditions,tedious synthetic methods and the requirement of specific m...Nitrogen-rich porous organic polymers(POPs)with basic features have already shown promising performance in various organic reactions.But the harsh conditions,tedious synthetic methods and the requirement of specific monomers impede their further application.Herein,we introduce isoindoline chemistry into POP community.An isoindoline formation process between aniline and bromomethylbenzenedcoupling nucleophilic substitution,HBr elimination,and intramolecular cyclization in one pot,is utilized for POPs synthesis.Nitrogen-rich isoindolinebased porous polymers(IPPs)were obtained with specific surface areas up to 408 m^(2) g^(-1).Unexpectedly,mechanochemistry could enable the rapid(3 h)and solid-state synthesis of IPP catalysts.Moreover,this nitrogen-rich catalyst presents excellent activity(isolated yield:99%),scalable ability(up to 14 g per run)and recyclability(five runs)towards the Knoevenagel condensation reaction under mild reaction conditions(water as solvent at room temperature).展开更多
The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Po...The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.展开更多
The development of reliable catalysts with both excellent activity and recyclability for carbon dioxide(CO_(2))hydrogenation is challenging.Herein,a ternary hybrid heterogeneous catalyst,involving mononuclear Ru compl...The development of reliable catalysts with both excellent activity and recyclability for carbon dioxide(CO_(2))hydrogenation is challenging.Herein,a ternary hybrid heterogeneous catalyst,involving mononuclear Ru complex,N,P-containing porous organic polymers(POPs),and mesoporous hollow carbon spheres(Ru^(3+)-POPs@MHCS)is reported for CO_(2)hydrogenation to formate.Based on comprehensive structural analyses,we demonstrated that Ru^(3+)-POPs were successfully immobilized within MHCS.The optimized Ru^(3+)-0.5POPs@MHCS catalyst,which was obtained with about 5 wt.%Ru^(3+)and 0.5 mmol POPs polymers confined into 0.3 g MHCS,exhibited high catalytic activity for CO_(2)hydrogenation to formate(turnover number(TON)>1,200 for 24 h under mild reaction conditions(4.0 MPa,120℃))and improved durability,compared to Ru^(3+)catalysts without POPs polymers(Ru^(3+)-MHCS)and unencapsulated MHCS(Ru^(3+)-0.5POPs)catalysts.The improved catalytic performance is attributed to the high surface area and large pore volume of MHCS which favors dispersion and stabilization of Ru^(3+)-POPs.Furthermore,the MHCS and POPs showed high CO_(2)adsorption ability.Ru^(3+)-POPs encapsulated into MHCS reduces the activation energy barrier for CO_(2)hydrogenation to formate.展开更多
Covalent organic frameworks(COFs)are nanoporous crystalline polymers with densely conjugated structures.This work discovers that imine-linked COFs exhibit remarkable photodegradation efficiency to azo dyes dissolved i...Covalent organic frameworks(COFs)are nanoporous crystalline polymers with densely conjugated structures.This work discovers that imine-linked COFs exhibit remarkable photodegradation efficiency to azo dyes dissolved in water.Visible light generates different types of radicals from COFs,and superoxide radicals break N=N bonds in dye molecules,resulting in 100%degradation of azo dyes within 1 h.In contrast,these dyes cannot be degraded by conventionally used photocatalysts,for example,TiO2.Importantly,the COF photocatalysts can be recovered from the dye solutions and re-used to degrade azo dyes for multiple times without loss of degradation efficiency.This work provides an efficient strategy to degrade synthetic dyes,and we expect that COFs with designable structures may use as new photocatalysts for other important applications.展开更多
Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materia...Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materials. Herein, we report an effective synthetic protocol to fabricate a new pyrylium-containing porous organic polymers(POPs), named TMP-P, via Knoevenagel condensation with 2,4,6-trimethylpyrylium salt(TMP) as the key building block and 1,4-phthalaldehyde as the linker. The resulting ionic polymer TMPP exhibited efficient visible-light-driven heterogeneous photodegradation of Rhodamine B, owing to the presence of wide visible light absorption and a narrow optical band gap triggered pyrylium core in the framework.展开更多
Porous organic polymers(POPs)containing catalytically active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear meta...Porous organic polymers(POPs)containing catalytically active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear metal species.Herein,we report the reaction between catechol-containing POPs(Cat-POPs)and[CuIMes]n to afford the corresponding Cu^(I)_(2)-CatPOPs with a putative vicinal binuclear(catecholate)Cu^(I)_(2)moiety.The resulting Cu^(I)_(2)-CatPOPs exhibit high Brunauer–Emmett–Teller surface areas,good stability,and excellent catalytic activity toward the aerobic oxidation of a broad range of primary and secondary alcohols under mild conditions,with either 2,2,6,6-tetramethylpiperidinyl-N-oxyl or 9-azabicyclo[3.3.0]nonane-N-oxyl as the cocatalyst.As green aerobic oxidation catalysts,the Cu^(I)_(2)-CatPOPs are much more active than the correspondingmononuclear CuIICatPOPs,where each catecholate moiety only supports one CuII center;CuI-ConPOPs,where the binding sites for CuI is a nonvicinal 1,4-dihydroxybenzene moiety;and the homogeneous analogue(3,6-di-tert-butyl catecholate)Cu^(I)_(2).These results are consistent with a proposed vicinal binuclear Cu^(I)_(2)structure that can efficiently activate molecular oxygen for the aerobic oxidation of alcohols,mechanistically similar to that observed in dicopper-containing oxygenases.Our results demonstrate the facile preparation of POPs with binuclear catalytically active sites that function as green heterogeneous catalysts for efficient oxidation of alcohols.展开更多
Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an eff...Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.展开更多
文摘Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis</span></span><span style="font-family:Verdana;">(</span><span style="font-family:Verdana;">isobutyronitrile</span><span style="font-family:Verdana;">)</span><span style="font-family:Verdana;"> (AIBN) at 60</span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration </span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">system</span><span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or </span><span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA</span><span style="font-family:Verdana;"> porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. The porous polymer was also obtained </span><span style="font-family:Verdana;">by</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">using</span><span style="font-family:""><span style="font-family:Verdana;"> a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of </span><span style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased</span><span style="font-family:Verdana;"> with </span><span style="font-family:Verdana;">increasing in the monomer concentration </span></span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction systems. Thioliso</span><span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 </span><span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate</span><span style="font-family:Verdana;"> (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and </span><i><span style="font-family:Verdana;">N,N</span></i><span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected </span><span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the</span><span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger </span><span style="font-family:Verdana;">than </span></span><span style="font-family:Verdana;">those</span><span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers</span><span style="font-family:Verdana;"> started at round 260</span><span style="font-family:Verdana;">°</span><span style="font-family:""><span style="font-family:Verdana;">C and showed </span><span style="font-family:Verdana;">endothermic peak at around 350</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C derived from degradation of </span><span style="font-family:Verdana;">thio-urethane bond.
基金National Natural Science Foundation of China,Grant/Award Numbers:21975096,22178280Key Laboratory of Nuclear Data Foundation,Grant/Award Number:JCKY2021201C151Young Talent Support Plan,Grant/Award Number:HG6J001。
文摘Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.
基金support of the National Science Foun-dation of China (Nos.21374024 and 61261130092)the Ministry of Science and Technology of China (Nos.2014CB932200 and 2011CB932500)is acknowledged.
文摘A series of benzimidazole-linked porous polymers are obtained by the condensation reaction between the o-aminobenzol end groups of building blocks(2,3,6,7,10,11-hexaaminotriphenylene,3,3'-diaminobenzidine or 1,2,4,5-benzenetetraamine)and the aldehyde groups of building blocks[terephthalicaldehyde,4,4'-biphenyl-dicarboxaldehyde,1,3,5-tris(4-acetylphenyl)benzene or 1,3,5-tris(4-formylbiphenyl)amine]in one-pot synthesis without employing any catalyst or template.The existence of the imidazole ring in the obtained polymers could be identified by Fourier transform infrared and solid-state^(13)C CP/MAS NMR spectroscopy.The sphere-shaped mor-phology of the obtained polymers is observed through scanning electron microscopy.The polymers possess Brunauer-Emmett-Teller specific surface area values over 600 m^(2)·g^(-1),showing hydrogen storage(up to 1.6 wt%,at 77 K and 1×10^(5)Pa)and carbon dioxide capture(up to 12.6 wt%,at 273 K and 1×10^(5)Pa)properties.Such poly-mers would possess good performance in the applications of gas storage and separation.
基金the National Natural Science Foundation of China(Nos.51776050 and 51536001).
文摘Micro/nano-porous polymeric material is considered a unique industrial material due to its extremelylow thermal conductivity, low density, and high surface area. Therefore, it is necessary to establishan accurate thermal conductivity prediction model suiting their applicable conditions and provide atheoretical basis for expanding their applications. In this work, the development of the calculationmodel of equivalent thermal conductivity of micro/nano-porous polymeric materials in recent yearsis summarized. Firstly, it reviews the process of establishing the overall equivalent thermal conductivity calculation model for micro/nanoporous polymers. Then, the predicted calculation models ofthermal conductivity are introduced separately according to the conductive and radiative thermalconductivity models. In addition, the thermal conduction part is divided into the gaseous thermalconductivity model, solid thermal conductivity model and gas-solid coupling model. Finally, it isconcluded that, compared with other porous materials, there are few studies on heat transfer of micro/nanoporous polymers, especially on the particular heat transfer mechanisms such as scale effectsat the micro/nanoscale. In particular, the following aspects of porous polymers still need to be furtherstudied: micro scaled thermal radiation, heat transfer characteristics of particular morphologies at thenanoscales, heat transfer mechanism and impact factors of micro/nanoporous polymers. Such studieswould provide a more accurate prediction of thermal conductivity and a broader application in energyconversion and storage systems.
基金financially supported by the Natural Science Foundation of China(no.21576059)the Key Technologies R&D Program(no.2011BAE06B02)+1 种基金the International Science&Technology Cooperation Program of China(2010DFB60840)the Science and Technology Project of Guizhou Province(nos.[2012]6012 and[2011]3016)
文摘In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural(EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran(THF). The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H(100) at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers(PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
基金supported by the National Natural Science Foundation of China(51422307,51372280,51232005)National Program for Support of Top-notch Young Professionals,Guangdong Natural Science Funds for Distinguished Young Scholar(S2013050014408),Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program(2014TQ01C337)+1 种基金Fundamental Research Funds for the Central Universities(15lgjc17)National Key Basic Research Program of China(2014CB932400)
文摘Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with zero-dimensional spherical shapes.However, owing to the limitations of synthetic methods, construction of porous building blocks in one dimension featuring high aspect ratios for porous nanonetwork structured polymer(PNSP) remains largely unexplored. Here we present the successful design and preparation of PNSP with a novel type of one-dimensional network unit, i.e., microporous heterogeneous nanowire. Well-defined core-shell polymer nanoobjects prepared from a gelable block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene are employed as building blocks, and facilely transformed into PNSP via hypercrosslinking of polystyrene shell. The as-prepared PNSP exhibits unique three-dimensional hierarchical nanonetwork morphologies with large surface area. These findings could provide a new avenue for fabrication of unique well-defined PNSP, and thus generate valuable breakthroughs in many applications.
基金supported by the National Natural Science Foundation of China(21474027,21574032)
文摘A series of thiophene-based conjugated microporous polymers(ThPOPs) have been synthesized on the basis of ferric chloride-catalyzed oxidative coupling polymerization of multi-thienyl monomers. The structures of ThPOPs were confirmed via solid-state 13 C CP/MAS NMR spectroscopy and Fourier-transform infrared spectroscopy. The ThPOPs possess high porosities and their high Brunauer-Emmett-Teller specific surface area results vary between 350 and 1320 m^2 g^(-1). The presence of abundant ultra-micropores at 0.50–0.63 nm allows ThPOPs efficient gas(carbon dioxide, methane, and hydrogen) adsorption.
文摘Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.
基金This work was supported by the National Key Research and Development Program of China(2016YFA0203200)the National Natural Science Foundation of China(21635007,21974134),K.C.Wong Education Foundation and Computing Centre of Jilin Province.
文摘The widespread use of bisphenol A(BPA)poses a serious threat to the environment and human health.However,efficient removal of BPA in water is incredibly challenging,owing to the inert chemical nature and electrical neutrality of BPA.In order to solve this problem,for the first time,we propose that a strategy of designing conjugated porous polymers with the pore size matching the size of BPA can greatly enhance the binding force of BPA.On this basis,we developed a novel conjugated poly 1,3,5-tri[4-(diphenylamino)phenyl]benzene(MPDPB)with intrinsic pore matching the size of BPA and multi-stage porous structure by editing polymerization with nitrobenzene.The binding energy of MPDPB to BPA is the highest at present(37.84 kcal/mol),which is 2.3 times that of the most powerful adsorbent previously reported and five times that of the conventional adsorbent.These advantages make MPDPB have super-high adsorption performance towards BPA and high absorbing stability under extreme environments.Impressively,MPDPB could be easily loaded on a non-woven fabric to generate point-of-use devices,which could eliminate more than 99.8%of BPA,making it the best BPA candidate adsorbent material.We believe that the proposed material design derived from the specific structure of the contaminant molecule can be extended to exploring further innovative adsorbents.
基金supported by the National Natural Science Foundation of China (Nos.21905072,22077025)the Natural Science Foundation of Hebei Province,China (Nos.B2020202062,B2020202086).
文摘Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO_(2)) capture. However, the regeneration of the CO_(2) still faces the problem of high energy cost. Here we synthesize a near-infrared region(NIR) light responsive conjugated porous polymer(PDPP-Gu) [DPP=3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] by constructing porous amorphous networks with a side chain engineering strategy to regulate CO_(2) adsorption and release through photothermal conversion. The PDPP-Gu is featured by a torsional conjugated backbone as well as a functional side chain of guanidino group. The donor-acceptor configuration of PDPP-Gu afforded strong absorption in the NIR and an excellent photothermal conversion capability of up to 48.8%, as well as a high surface energy. Moreover, guanidine modified side chain further enhanced the CO_(2)-polymers interactions, resulting in a high CO_(2) selective adsorption capacity(0.8 mmol/g) at 273 K, 1 bar(1 bar=105 Pa). The adsorbed CO_(2) can be released under NIR light irradiation. This strategy of molecule design combined the dual features of photothermal conversion and gas adsorption, which is beneficial for the development of materials to dynamically control the adsorption and release of CO_(2) through NIR light.
基金the National Natural Science Foundation of China (21871104, 21621001 and U1967215)the 111 project the Ministry of Education of China (B17020)
文摘Nitrogen-rich porous organic polymers have shown great potentials in gas adsorption/separation,photocatalysis,electrochemistry,sensing and so on.Herein,1,2,3-triazole functionalized triazine-based porous organic polymers(TT-POPs)have been synthesized by the copper-catalyzed azide-alkyne cycloaddition(Cu-AAC)polymerization reactions of 1,3,5-tris(4-azidophenyl)-triazine with 1,4-diacetylene benzene and 1,3,5-triacetylenebenzene,respectively.The characterizations of N2 adsorption at 77 K show TTPOPs possess permanent porosity with BET surface areas of 666 m^(2)·g^(-1)(TT-POP-1)and 406 m^(2)·g^(-1)(TT-POP-2).The adsorption capacities of TT-POPs for CO_(2),CH4,C2H2 and C2H4,as well as the selective separation abilities of CO_(2)/N2,CO_(2)/CH_(4),C_(2)H_(2)/CH_(4) and C_(2)H_(4)/CH_(4) were evaluated.The gas selective separation ratio of TT-POPs was calculated by the ideal adsorbed solution theory(IAST)method,wherein the selective separation ratios of C_(2)H_(2)/CH_(4) and C_(2)H_(4)/CH_(4) of TT-POP-2 was 48.4 and 13.6(298 K,0.1 MPa),which is comparable to other adsorbents(5.6–120.6 for C_(2)H_(2)/CH_(4),10–26 for C_(2)H_(4)/CH_(4)).This work shows that the 1,2,3-triazole functionalized triazine-based porous organic polymer has a good application prospect in natural gas purification.
基金funded by National Key Research and Development Program of China (2021YFC2101202)Bingtuan Science and Technology Program (2022DB025)+3 种基金Beijing Natural Science Foundation (2222015)Hebei Province Key Research and Development Program (21327316D)China Postdoctoral Science Foundation (2021M700011)the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of China。
文摘Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct method for obtaining the high flux is to decrease membrane thickness.Polyamide(PA)nanofiltration membrane is conventionally prepared by the direct interfacial polymerization(IP)on substrate surface,and results in a thick PA layer.In this work,we proposed a strategy that constructing triazine-based porous organic polymer(TRZ-POP)as the interlayer to prepare the ultrathin PA nanofiltration membranes.TRZ-POP is firstly deposited on the polyethersulfone substrate,and then the formed TRZ-POP provides more adhesion sites towards PA based on its high specific surface areas.The chemical bonding between terminal amine group of TRZ-POP and the amide group of PA further improves the binding force,and strengthens the stability of PA layer.More importantly,the high porosity of TRZPOP layer causes the higher polymerization of initial PA owning to the stored sufficient amino monomer;and H-bonding interaction between amine groups of TRZ-POP and piperazine(PIP)can astrict the release of PIP.Thus,IP process is controlled,and the thinnest thickness of prepared PA layer is only<15 nm.As expected,PA/TRZ-POP membrane shows a more excellent water flux of 1414 L·m^(-2)·h^(-1)·MPa^(-1)than that of the state-of-the-art nanofiltration membranes,and without sacrificing dye rejection.The build of TRZPOP interlayer develops a new method for obtaining a high-flux nanofiltration membrane.
基金supported by the National Natural Science Foundation of China(21731002,21975104,22101099,22150004,22271120)Guangdong Major Project of Basic and Applied Research(2019B030302009)+1 种基金the Outstanding Innovative Talents Cultivation Funded Programs for Doctoral Students of Jinan University(2022CXB007)the Fundamental Research Funds for the Central Universities and Jinan University(21621035)。
文摘Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.
基金Thousand Talent Program,National Natural Science Foundation of China(Grant No.21776174)the Open Foundation of the State Key Laboratory of Ocean Engineering(Shanghai Jiao Tong University of China)(No.1809)China Shipbuilding Industry Corporation for the support.
文摘Nitrogen-rich porous organic polymers(POPs)with basic features have already shown promising performance in various organic reactions.But the harsh conditions,tedious synthetic methods and the requirement of specific monomers impede their further application.Herein,we introduce isoindoline chemistry into POP community.An isoindoline formation process between aniline and bromomethylbenzenedcoupling nucleophilic substitution,HBr elimination,and intramolecular cyclization in one pot,is utilized for POPs synthesis.Nitrogen-rich isoindolinebased porous polymers(IPPs)were obtained with specific surface areas up to 408 m^(2) g^(-1).Unexpectedly,mechanochemistry could enable the rapid(3 h)and solid-state synthesis of IPP catalysts.Moreover,this nitrogen-rich catalyst presents excellent activity(isolated yield:99%),scalable ability(up to 14 g per run)and recyclability(five runs)towards the Knoevenagel condensation reaction under mild reaction conditions(water as solvent at room temperature).
基金supported by the National Key Research and Development Program of China(2017YFE0113500)the National Natural Science Foundation of China(51872027)。
文摘The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.
基金supported by JSPS KAKENHI(Nos.18K14056 and 19H00838)JST,PRESTO(No.JPMJPR19T3)+3 种基金Japan.A part of this work was supported by the cooperative research program of“Network Joint Research Center for Materials and Devices”(No.20211069).support of the International Joint Research Promotion Program at Osaka University.G.X.Y.gratefully acknowledges the financial support from the China Scholarship Council(No.201808310132)Y.K.,K.M.,and H.Y.thank the Elements Strategy Initiative of MEXT(No.JPMXP0112101003)Japan.The synchrotron radiation experiments for XAFS measurement were performed at the BL01B1 beamline in SPring-8 with approval from JASRI(Nos.2019B1114 and 2020A1064).
文摘The development of reliable catalysts with both excellent activity and recyclability for carbon dioxide(CO_(2))hydrogenation is challenging.Herein,a ternary hybrid heterogeneous catalyst,involving mononuclear Ru complex,N,P-containing porous organic polymers(POPs),and mesoporous hollow carbon spheres(Ru^(3+)-POPs@MHCS)is reported for CO_(2)hydrogenation to formate.Based on comprehensive structural analyses,we demonstrated that Ru^(3+)-POPs were successfully immobilized within MHCS.The optimized Ru^(3+)-0.5POPs@MHCS catalyst,which was obtained with about 5 wt.%Ru^(3+)and 0.5 mmol POPs polymers confined into 0.3 g MHCS,exhibited high catalytic activity for CO_(2)hydrogenation to formate(turnover number(TON)>1,200 for 24 h under mild reaction conditions(4.0 MPa,120℃))and improved durability,compared to Ru^(3+)catalysts without POPs polymers(Ru^(3+)-MHCS)and unencapsulated MHCS(Ru^(3+)-0.5POPs)catalysts.The improved catalytic performance is attributed to the high surface area and large pore volume of MHCS which favors dispersion and stabilization of Ru^(3+)-POPs.Furthermore,the MHCS and POPs showed high CO_(2)adsorption ability.Ru^(3+)-POPs encapsulated into MHCS reduces the activation energy barrier for CO_(2)hydrogenation to formate.
基金financially supported by the National Science Fund for Distinguished Young Scholars (21825803)the Program of Excellent Innovation Teams of Jiangsu Higher Education Institutions and the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘Covalent organic frameworks(COFs)are nanoporous crystalline polymers with densely conjugated structures.This work discovers that imine-linked COFs exhibit remarkable photodegradation efficiency to azo dyes dissolved in water.Visible light generates different types of radicals from COFs,and superoxide radicals break N=N bonds in dye molecules,resulting in 100%degradation of azo dyes within 1 h.In contrast,these dyes cannot be degraded by conventionally used photocatalysts,for example,TiO2.Importantly,the COF photocatalysts can be recovered from the dye solutions and re-used to degrade azo dyes for multiple times without loss of degradation efficiency.This work provides an efficient strategy to degrade synthetic dyes,and we expect that COFs with designable structures may use as new photocatalysts for other important applications.
基金financial support from the Natural Science Foundation of Liaoning Province (No. 2019-MS-046)。
文摘Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materials. Herein, we report an effective synthetic protocol to fabricate a new pyrylium-containing porous organic polymers(POPs), named TMP-P, via Knoevenagel condensation with 2,4,6-trimethylpyrylium salt(TMP) as the key building block and 1,4-phthalaldehyde as the linker. The resulting ionic polymer TMPP exhibited efficient visible-light-driven heterogeneous photodegradation of Rhodamine B, owing to the presence of wide visible light absorption and a narrow optical band gap triggered pyrylium core in the framework.
基金support from the National Natural Science Foundation of China(no.52103328)the Guangdong Basic and Applied Basic Research Foundation(no.2020A1515110575)the Science and Technology Program of Guangzhou(no.202102020422),and the Sun Yat-sen University Start-up Funding.S.T.N.is grateful for the financial support from DTRA(no.HDTRA1-14-1-0014),the U.S.Department of Energy(DOE)(no.DE FG02-03-ER154757 to the Institute of Catalysis for Energy Processes(ICEP)at Northwestern University).Work at Argonne National Laboratory was supported by the U.S.Department of Energy(DOE),Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,and Biosciences,under Contract DEAC02-06CH11357.Experimental facilities at the Integrated Molecular Structure Education and Research Center(IMSERC)and the Northwestern University Atomic and Nanoscale Characterization Experimental Center(EPIC,Keck-II)at Northwestern University(NU)were purchased with grants from NSFNSEC,NSF-MRSEC,the Keck Foundation,the state of Illinois,and Northwestern University.ICP-OES analyses were carried out at the Northwestern University Quantitative Bio-element Imaging Center.
文摘Porous organic polymers(POPs)containing catalytically active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear metal species.Herein,we report the reaction between catechol-containing POPs(Cat-POPs)and[CuIMes]n to afford the corresponding Cu^(I)_(2)-CatPOPs with a putative vicinal binuclear(catecholate)Cu^(I)_(2)moiety.The resulting Cu^(I)_(2)-CatPOPs exhibit high Brunauer–Emmett–Teller surface areas,good stability,and excellent catalytic activity toward the aerobic oxidation of a broad range of primary and secondary alcohols under mild conditions,with either 2,2,6,6-tetramethylpiperidinyl-N-oxyl or 9-azabicyclo[3.3.0]nonane-N-oxyl as the cocatalyst.As green aerobic oxidation catalysts,the Cu^(I)_(2)-CatPOPs are much more active than the correspondingmononuclear CuIICatPOPs,where each catecholate moiety only supports one CuII center;CuI-ConPOPs,where the binding sites for CuI is a nonvicinal 1,4-dihydroxybenzene moiety;and the homogeneous analogue(3,6-di-tert-butyl catecholate)Cu^(I)_(2).These results are consistent with a proposed vicinal binuclear Cu^(I)_(2)structure that can efficiently activate molecular oxygen for the aerobic oxidation of alcohols,mechanistically similar to that observed in dicopper-containing oxygenases.Our results demonstrate the facile preparation of POPs with binuclear catalytically active sites that function as green heterogeneous catalysts for efficient oxidation of alcohols.
基金the National Natural Science Foundation of China(No.U1808210)the Natural Science Foundation of Liaoning province(No.2019-MS-046).
文摘Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.