The isolation of graphene and subsequent studies showed that obtaining atomically thin crystalline sheets was feasible and possessed extraordinary properties.This result opened the door to an entirely new family of ma...The isolation of graphene and subsequent studies showed that obtaining atomically thin crystalline sheets was feasible and possessed extraordinary properties.This result opened the door to an entirely new family of materials known as two-dimensional or 2D materials.Research in this field is intense:the emergence of new 2D materials,the properties of their combinations and the ability of graphene to reinvent itself,showing novel and exciting properties,make it likely that this field will continue to be one of the leading topics of materials science and condensed matter physics.展开更多
The application of organic photocatalysts towards the oxidation of pollutants in water is hampered by different limitations such as their insolubility in the media.Herein,we report that the grafting of a photoorganoca...The application of organic photocatalysts towards the oxidation of pollutants in water is hampered by different limitations such as their insolubility in the media.Herein,we report that the grafting of a photoorganocatalyst into mesoporous silica materials is an ideal approach to obtain effective catalysts.Thereby,the photocatalyst 10-phenylphenothiazine(PTH)was easily anchored into three different mesoporous silica-based materials(MSN,MSU-2 and SBA-15)with different particle sizes and pore sizes through an amide bond formation.The materials were characterized using IR analysis,solid-state X-ray diffraction,porosity and microscopy(SEM and TEM)techniques,showing that PTH is immobilized inside the pores of the materials and its optical properties are maintained after the anchoring.Although homogeneous PTH was inactive in water media,the three photocatalytic materials were active for the degradation of pollutants.SBA-15-AP-PTH exhibited the highest catalytic performance towards the degradation of acetaminophen and diclofenac under solar irradiation,finding in this manner a new strategy for the decontamination of pollutants.展开更多
A novel porous and crystalline two-dimensional(2D)electrochemically active covalent organic framework(COF)based on ortho-quinone units has been prepared as an innovative approach towards the development of organic cat...A novel porous and crystalline two-dimensional(2D)electrochemically active covalent organic framework(COF)based on ortho-quinone units has been prepared as an innovative approach towards the development of organic cathode materials with multiple redox sites as an efficient electrocatalyst for the oxygen reduction reaction(ORR).In contrast with most of the previously reported COFs as electrocatalysts for the ORR,the electrocatalytic application of this material towards ORR has been investigated without adding any metal or conductive supporting material and avoiding any additional carbonization step.Additionally,the electrochemical properties of the COF material have been compared with two analogue amorphous frameworks with similar chemical composition,which points out the important role of the enhanced crystallinity and porosity of the COF network in its superior performance as an electrocatalyst towards ORR.展开更多
A well-established strategy to synthesize heterogeneous,metal-organic framework(MOF)catalysts that exhibit nanoconfinement effects,and specific pores with highly-localized catalytic sites,is to use organic linkers con...A well-established strategy to synthesize heterogeneous,metal-organic framework(MOF)catalysts that exhibit nanoconfinement effects,and specific pores with highly-localized catalytic sites,is to use organic linkers containing organocatalytic centers.Here,we report that by combining this linker approach with reticular chemistry,and exploiting three-dimensioanl(3D)MOF-structural data from the Cambridge Structural Database,we have designed four heterogeneous MOF-based catalysts for standard organic transformations.These programmable MOFs are isoreticular versions of pcu IRMOF-16,feu UiO-68 and pillared-pcu SNU-8X,the three most common topologies of MOFs built from the organic linker p.p'-terphenyldicarboxylic acid(tpdc).To synthesize the four squaramide-based MOFs,we designed and synthesized a linker,4,4’-((3,4-dioxocyclobut-1-ene-1,2-diyl)bis(azanedyil))dibenzoic acid(Sq_tpdc),which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers.Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena.Therefore,the four MOFs share the same organocatalytic squaramide moiety,but confine it within distinct pore environments.We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations:a Friedel-Crafts alkylation and an epoxide ring-opening.Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.展开更多
In the present work we develop an electrochemical assisted method to form nanopores on the surface of highly oriented pyrolytic graphite(HOPG),which was accomplished by a simple electrochemical route and a scalable na...In the present work we develop an electrochemical assisted method to form nanopores on the surface of highly oriented pyrolytic graphite(HOPG),which was accomplished by a simple electrochemical route and a scalable nanomaterial,carbon nanodots,without applying high voltages,high temperatures or toxic reagents.HOPG electrodes are in a solution of N-enrich carbon nanodots in acidic media and the potential scans applied on HOPG lead to the formation of a spatially inhomogeneous porous surface.The diameter of the resulting nanopores can be tuned by controlling the number of electrochemical reduction cycles.The resulting nanoporous surfaces are characterized by atomic force microscopy,Raman spectroscopy,scanning electrochemical microscopy,electrochemical impedance spectroscopy and electrochemistry.These nanoporous HOPG showed high capacitance.Hence the potential of these surfaces to the development of energy storage devices is demonstrated.展开更多
文摘The isolation of graphene and subsequent studies showed that obtaining atomically thin crystalline sheets was feasible and possessed extraordinary properties.This result opened the door to an entirely new family of materials known as two-dimensional or 2D materials.Research in this field is intense:the emergence of new 2D materials,the properties of their combinations and the ability of graphene to reinvent itself,showing novel and exciting properties,make it likely that this field will continue to be one of the leading topics of materials science and condensed matter physics.
基金financially supported by the European Research Council(ERC-Co G,No.647550)Spanish Government(No.RTI2018095038-B-I00)Spanish State Research Agency(No.PID2019106186RB-I00/AEI/10.13039/501100011033)。
文摘The application of organic photocatalysts towards the oxidation of pollutants in water is hampered by different limitations such as their insolubility in the media.Herein,we report that the grafting of a photoorganocatalyst into mesoporous silica materials is an ideal approach to obtain effective catalysts.Thereby,the photocatalyst 10-phenylphenothiazine(PTH)was easily anchored into three different mesoporous silica-based materials(MSN,MSU-2 and SBA-15)with different particle sizes and pore sizes through an amide bond formation.The materials were characterized using IR analysis,solid-state X-ray diffraction,porosity and microscopy(SEM and TEM)techniques,showing that PTH is immobilized inside the pores of the materials and its optical properties are maintained after the anchoring.Although homogeneous PTH was inactive in water media,the three photocatalytic materials were active for the degradation of pollutants.SBA-15-AP-PTH exhibited the highest catalytic performance towards the degradation of acetaminophen and diclofenac under solar irradiation,finding in this manner a new strategy for the decontamination of pollutants.
基金This work was financially supported by MICINN(Nos.PID2019-106268GB-C33,CTQ2017-84309-C2-1-R,RED2018-102412-T,and FIS2017-82415-R)Comunidad Autónoma de Madrid Transnanoavansens Program(No.S2018/NMT-4349)。
文摘A novel porous and crystalline two-dimensional(2D)electrochemically active covalent organic framework(COF)based on ortho-quinone units has been prepared as an innovative approach towards the development of organic cathode materials with multiple redox sites as an efficient electrocatalyst for the oxygen reduction reaction(ORR).In contrast with most of the previously reported COFs as electrocatalysts for the ORR,the electrocatalytic application of this material towards ORR has been investigated without adding any metal or conductive supporting material and avoiding any additional carbonization step.Additionally,the electrochemical properties of the COF material have been compared with two analogue amorphous frameworks with similar chemical composition,which points out the important role of the enhanced crystallinity and porosity of the COF network in its superior performance as an electrocatalyst towards ORR.
基金the Spanish MINECO(projects RTI2018-095622-B-I00,RTI2018-095038-B-I00)the Catalan AGAUR(project 2017 SGR 238)+1 种基金the ERC under the EU FP7(ER C-Co 615954)European Unions Horizon 2020 research and innovation program under grant agreement No.685727,and European Structural Funds(S2018/NMT-4367).It was alsofunded by the CERCA Program/Generalitat de Catalunya.ICN2 is supported by the Severo Ochoa program from the Spanish MINECO(G rant No.SEV-2017-0706).
文摘A well-established strategy to synthesize heterogeneous,metal-organic framework(MOF)catalysts that exhibit nanoconfinement effects,and specific pores with highly-localized catalytic sites,is to use organic linkers containing organocatalytic centers.Here,we report that by combining this linker approach with reticular chemistry,and exploiting three-dimensioanl(3D)MOF-structural data from the Cambridge Structural Database,we have designed four heterogeneous MOF-based catalysts for standard organic transformations.These programmable MOFs are isoreticular versions of pcu IRMOF-16,feu UiO-68 and pillared-pcu SNU-8X,the three most common topologies of MOFs built from the organic linker p.p'-terphenyldicarboxylic acid(tpdc).To synthesize the four squaramide-based MOFs,we designed and synthesized a linker,4,4’-((3,4-dioxocyclobut-1-ene-1,2-diyl)bis(azanedyil))dibenzoic acid(Sq_tpdc),which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers.Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena.Therefore,the four MOFs share the same organocatalytic squaramide moiety,but confine it within distinct pore environments.We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations:a Friedel-Crafts alkylation and an epoxide ring-opening.Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.
基金The authors are grateful for the financial support provided by the Ministerio de Ciencia,Innovación,Universidades of Spain(CTQ2017-84309-C2-1-R,RED2018-102412-T)Comunidad Autónoma de Madrid(TRANSNANOAVANSENS Program)+1 种基金Generalitat Valenciana(APOSTD/2017/010)C.G.-S.also acknowledges the financial support from the Comunidad Autónoma de Madrid,Atracción de Talento Program(2017-T1/BIO-5435).
文摘In the present work we develop an electrochemical assisted method to form nanopores on the surface of highly oriented pyrolytic graphite(HOPG),which was accomplished by a simple electrochemical route and a scalable nanomaterial,carbon nanodots,without applying high voltages,high temperatures or toxic reagents.HOPG electrodes are in a solution of N-enrich carbon nanodots in acidic media and the potential scans applied on HOPG lead to the formation of a spatially inhomogeneous porous surface.The diameter of the resulting nanopores can be tuned by controlling the number of electrochemical reduction cycles.The resulting nanoporous surfaces are characterized by atomic force microscopy,Raman spectroscopy,scanning electrochemical microscopy,electrochemical impedance spectroscopy and electrochemistry.These nanoporous HOPG showed high capacitance.Hence the potential of these surfaces to the development of energy storage devices is demonstrated.