Optical nanoparticles are nowadays one of the key elements of photonics.They do not only allow optical imaging of a plethora of systems(from cells to microelectronics),but,in many cases,they also behave as highly sens...Optical nanoparticles are nowadays one of the key elements of photonics.They do not only allow optical imaging of a plethora of systems(from cells to microelectronics),but,in many cases,they also behave as highly sensitive remote sensors.In recent years,it has been demonstrated the success of optical tweezers in isolating and manipulating individual optical nanoparticles.This has opened the door to high resolution single particle scanning and sensing.In this quickly growing field,it is now necessary to sum up what has been achieved so far to identify the appropriate system and experimental set-up required for each application.In this review article we summarize the most relevant results in the field of optical trapping of individual optical nanoparticles.After systematic bibliographic research,we identify the main families of optical nanoparticles in which optical trapping has been demonstrated.For each case,the main advances and applications have been described.Finally,we also include our critical opinion about the future of the field,identifying the challenges that we are facing.展开更多
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
Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,co...Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,compounds structurally related to porphyrins,have emerged as promising solar cell candidates.In contrast to the widely used fullerene acceptors,porphyrinoids exhibit strong,broad absorption properties across the UV–vis/NIR spectrum,which can be easily tuned through chemical modifications.Furthermore,they can be prepared and derivatized using cost-effective and straightforward methodologies,allowing for convenient adjustments in thin-film morphology,processability,supramolecular organization,and energy levels.Additionally,these compounds offer higher thermal and photochemical stability,resulting in longer device lifetimes compared to their fullerene-based counterparts.In this review,we outline the utilization of porphyrinoids as NFAs in OSCs and PSCs,discussing essential aspects such as design guidelines,molecular properties,and device configuration.Our goal is to inspire and further promote the development of n-type porphyrinoids,which have not yet fully unleashed their potential.展开更多
The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordin...The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.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
1 Results Recently increased interest is shown to proton conducting materials based on the alkaline polymer-inorganic acid complexes that is caused by a possibility of their application as the high-temperature electro...1 Results Recently increased interest is shown to proton conducting materials based on the alkaline polymer-inorganic acid complexes that is caused by a possibility of their application as the high-temperature electrolyte systems for various electrochemical devices (fuel cells,sensors,lithium power sources etc.).Complexes of inorganic acids with the alkaline polymers (polybenzimidazoles[1],polyvinylpyridines[2]) are characterized by high ionic conductivity at ambient temperatures (up to 10-2 Ω-1·cm-1) a...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
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
基金supported by projects PID2019-106211RB-I00,PID2019-105195RA-I00,and PID2021-123228NB-I00funded by MCIN/AEI/10.13039/501100011033 and projects CNS2022-135495,and TED2021-129937B-I00 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGeneration EU/PRTR.P.Camarero thanks Comunidad de Madrid for Programa Investigo by Plan de Recuperación,Transformación y Resiliencia-Comunidad de Madrid-Ministerio de Trabajo y Economía Social de España-Unión Europea-NextGenerationEU.F.Zhang acknowledges the scholarship from the China Scholarship Council (202108440235)supported by Comunidad de Madrid (S2022/BMD-7403 RENIM-CM and REACT-UCM projects).
文摘Optical nanoparticles are nowadays one of the key elements of photonics.They do not only allow optical imaging of a plethora of systems(from cells to microelectronics),but,in many cases,they also behave as highly sensitive remote sensors.In recent years,it has been demonstrated the success of optical tweezers in isolating and manipulating individual optical nanoparticles.This has opened the door to high resolution single particle scanning and sensing.In this quickly growing field,it is now necessary to sum up what has been achieved so far to identify the appropriate system and experimental set-up required for each application.In this review article we summarize the most relevant results in the field of optical trapping of individual optical nanoparticles.After systematic bibliographic research,we identify the main families of optical nanoparticles in which optical trapping has been demonstrated.For each case,the main advances and applications have been described.Finally,we also include our critical opinion about the future of the field,identifying the challenges that we are facing.
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T.T.acknowledges financial support from the Spanish MCIN/AEI/10.13039/501100011033(PID2020-116490GBI00,TED2021-131255B-C43)the Comunidad de Madrid and the Spanish State through the Recovery,Transformation and Resilience Plan[“Materiales Disruptivos Bidimensionales(2D)”(MAD2D-CM)(UAM1)-MRR Materiales Avanzados]+2 种基金the European Union through the Next Generation EU funds.Instituto madrileno de estudios avanzados Nanociencia acknowledges support from the“Severo Ochoa”Programme for Centres of Excellence in R&D(Ministerio de asuntos economicos y transformacion digital,Grant SEV2016-0686)T.T.also acknowledges the Alexander von Humboldt Foundation(Germany)for the A.v.Humboldt-J.C.Mutis Research Award 2023(Ref 3.3-1231125-ESP-GSA)J.L.acknowledgesMinisterio de Eduacion,Cultura y Deporte(MECD),Spain,for an F.P.U.Fellowship.
文摘Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,compounds structurally related to porphyrins,have emerged as promising solar cell candidates.In contrast to the widely used fullerene acceptors,porphyrinoids exhibit strong,broad absorption properties across the UV–vis/NIR spectrum,which can be easily tuned through chemical modifications.Furthermore,they can be prepared and derivatized using cost-effective and straightforward methodologies,allowing for convenient adjustments in thin-film morphology,processability,supramolecular organization,and energy levels.Additionally,these compounds offer higher thermal and photochemical stability,resulting in longer device lifetimes compared to their fullerene-based counterparts.In this review,we outline the utilization of porphyrinoids as NFAs in OSCs and PSCs,discussing essential aspects such as design guidelines,molecular properties,and device configuration.Our goal is to inspire and further promote the development of n-type porphyrinoids,which have not yet fully unleashed their potential.
基金financial support from the Russian Science Foundation (project N 21-13-00221)for the synthesis and studies of optical and magnetic properties of 1supported by the Ministry of Science and Higher Education of the Russian Federation (Registration number 124013100858-3)+2 种基金E.N.I.and M.K.I.acknowledge Grant from the Ministry of Science and Higher Education of the Russian Federation (no.075-15-2021-579)for synthesis of H3Hhp and preliminary DFT calculationssupport from the Spanish MCIN/AEI/10.13039/501100011033 (PID2020-116490GB-I00,TED2021-131255B-C43)the Comunidad de Madrid,and the Spanish State through the Recovery,Transformation and Resilience Plan[“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados],and the European Union through the Next Generation EU funds.Instituto madrileno de estudios avanzados Nanociencia acknowledges support from the“Severo Ochoa”Programme for Centres of Excellence in R&D (Ministerio de asuntos economicos y transformacion digital,Grant SEV2016-0686).
文摘The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.
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.
文摘1 Results Recently increased interest is shown to proton conducting materials based on the alkaline polymer-inorganic acid complexes that is caused by a possibility of their application as the high-temperature electrolyte systems for various electrochemical devices (fuel cells,sensors,lithium power sources etc.).Complexes of inorganic acids with the alkaline polymers (polybenzimidazoles[1],polyvinylpyridines[2]) are characterized by high ionic conductivity at ambient temperatures (up to 10-2 Ω-1·cm-1) a...
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.
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.