Imparting one-dimensional(1D)ultrafine organic nanowires with tailored ligands and atomically-dispersed central noble metal to craft high-performance hybrid single atom electrocatalysts offers a prospective yet challe...Imparting one-dimensional(1D)ultrafine organic nanowires with tailored ligands and atomically-dispersed central noble metal to craft high-performance hybrid single atom electrocatalysts offers a prospective yet challenging approach for the advancement in hydrogen evolution reactions(HER).Herein,we report the evaporation-induced self-assembly of sequence-defined amphiphilic alternating azopeptoids(AAAPs)to generate photo-responsive and micron-scale ultrafine peptoid nanowires(UFPNWs)with a diameter of~1.8 nm via pendants'hydrophobic conjugate stacking mechanism,exemplifying the finest biomimetic polymers-based nanowires to date.A series of 1D UFPNWs-based single-atom catalysts(SACs)were meticulously fabricated using the chelation interaction between Pt ions and nitrogenous ligands.The photo-controllable electrocatalytic performance was evaluated toward acidic HER,which was highly dependent on the presence of Pt elements,the structural characteristic of supports,and the peripheral coordination microenvironment of the center Pt atoms.Notably,the Pt-based hybrid SACs using terpyridine-modified UFPNWs as support presented favorable electrocatalytic capacity with an overpotential of~20 m V at a current density of 10 m A cm^(-2),and a mass activity of 89.6 times greater than commercial Pt/C catalyst.Our work paves an appealing avenue for the construction of stimuli-responsive 1D organic nanowire-based hybrid catalysts with controllable electrocatalytic HER performance.展开更多
Artificial vesicles for mimicking the unique structures and functions of natural organelles represent a promising scientific object in biomimicry.However,the development of the stimuli-responsive and ultrathin vesicle...Artificial vesicles for mimicking the unique structures and functions of natural organelles represent a promising scientific object in biomimicry.However,the development of the stimuli-responsive and ultrathin vesicles assembled from sequence-defined biomimetic polymers for controllable applications is still a significant challenge.Herein,we report the self-assembly of azobenzene-based amphiphilic alternating peptoids to generate photo-responsive and ultrathin peptoid vesicle(pepsomes)with an average diameter of∼180 nm.Both cryo-transmission electron microscopy(TEM)and dissipative particle dynamics simulation proved that the vesicular membrane was the ultrathin bilayer structure around∼1.6 nm.The photo-responsive ability of pepsomes was demonstrated by the reversible size changes upon the alternative irradiation with ultraviolet(UV)and visible lights,which was attributable to the photoisomerization virtue of azobenzene moiety.As a proof-of-concept,the photo-controllable catalytic action of gold nanoparticles-decorated pepsomes was evaluated toward the borohydride-mediated reduction from 4-nitrophenol to 4-aminophenol.Photo-controllable reversible and recyclable catalytic activity was effectively modulated using the alternative irradiation with UV and visible lights for five cycles.Our work provides a simple strategy to prepare stimuli-responsive and ultrathin vesicles for potential application on nanocatalysis.展开更多
The development of artificial light-harvesting systems based on long-range ordered ultrathin organic nanomaterials(i.e., below3 nm), which were assembled from stimuli-responsive sequence-controlled biomimetic polymers...The development of artificial light-harvesting systems based on long-range ordered ultrathin organic nanomaterials(i.e., below3 nm), which were assembled from stimuli-responsive sequence-controlled biomimetic polymers, remains challenging. Herein,we report the self-assembly of azobenzene-containing amphiphilic ternary alternating peptoids to construct photo-responsive ultrathin peptoids nanoribbons(UTPNRs) with a thickness of ~2.3 nm and the length in several micrometers. The pendants hydrophobic conjugate stacking mechanism explained the formation of one-dimensional ultrathin nanostructures, whose thickness was highly dependent on the length of side groups. The photo-isomerization of azobenzene moiety endowed the aggregates with a reversible morphology transformation from UTPNRs to spherical micelles(46.5 nm), upon the alternative irradiation with ultraviolet and visible light. Donor of 4-(2-hydroxyethylamino)-7-nitro-2,1,3-benzoxadiazole(NBD) and acceptor of rhodamine B(RB) were introduced onto the hydrophobic and hydrophilic regions, respectively, to generate photocontrollable artificial light-harvesting systems. Compared with the spheres-based systems, the obtained NBD-UTPNRs@RB composite proved a higher energy transfer efficiency(90.6%) and a lower requirement of RB acceptors in water. A proof-ofconcept use as fluorescent writable ink demonstrated the potential of UTPNRs on information encryption.展开更多
基金supported by the National Natural Science Foundation of China(52373114,52073092,22231007,22001071)。
文摘Imparting one-dimensional(1D)ultrafine organic nanowires with tailored ligands and atomically-dispersed central noble metal to craft high-performance hybrid single atom electrocatalysts offers a prospective yet challenging approach for the advancement in hydrogen evolution reactions(HER).Herein,we report the evaporation-induced self-assembly of sequence-defined amphiphilic alternating azopeptoids(AAAPs)to generate photo-responsive and micron-scale ultrafine peptoid nanowires(UFPNWs)with a diameter of~1.8 nm via pendants'hydrophobic conjugate stacking mechanism,exemplifying the finest biomimetic polymers-based nanowires to date.A series of 1D UFPNWs-based single-atom catalysts(SACs)were meticulously fabricated using the chelation interaction between Pt ions and nitrogenous ligands.The photo-controllable electrocatalytic performance was evaluated toward acidic HER,which was highly dependent on the presence of Pt elements,the structural characteristic of supports,and the peripheral coordination microenvironment of the center Pt atoms.Notably,the Pt-based hybrid SACs using terpyridine-modified UFPNWs as support presented favorable electrocatalytic capacity with an overpotential of~20 m V at a current density of 10 m A cm^(-2),and a mass activity of 89.6 times greater than commercial Pt/C catalyst.Our work paves an appealing avenue for the construction of stimuli-responsive 1D organic nanowire-based hybrid catalysts with controllable electrocatalytic HER performance.
基金supported by the National Natural Science Foundation of China(52073092,22001071,51873061)Shanghai Scientific and Technological Innovation Projects(19JC1411700,18JC1410802)。
文摘Artificial vesicles for mimicking the unique structures and functions of natural organelles represent a promising scientific object in biomimicry.However,the development of the stimuli-responsive and ultrathin vesicles assembled from sequence-defined biomimetic polymers for controllable applications is still a significant challenge.Herein,we report the self-assembly of azobenzene-based amphiphilic alternating peptoids to generate photo-responsive and ultrathin peptoid vesicle(pepsomes)with an average diameter of∼180 nm.Both cryo-transmission electron microscopy(TEM)and dissipative particle dynamics simulation proved that the vesicular membrane was the ultrathin bilayer structure around∼1.6 nm.The photo-responsive ability of pepsomes was demonstrated by the reversible size changes upon the alternative irradiation with ultraviolet(UV)and visible lights,which was attributable to the photoisomerization virtue of azobenzene moiety.As a proof-of-concept,the photo-controllable catalytic action of gold nanoparticles-decorated pepsomes was evaluated toward the borohydride-mediated reduction from 4-nitrophenol to 4-aminophenol.Photo-controllable reversible and recyclable catalytic activity was effectively modulated using the alternative irradiation with UV and visible lights for five cycles.Our work provides a simple strategy to prepare stimuli-responsive and ultrathin vesicles for potential application on nanocatalysis.
基金supported by the National Natural Science Foundation of China (22001071, 52373114, 52073092, 52325308)Shanghai Scientific and Technological Innovation Project(19JC1411700)。
文摘The development of artificial light-harvesting systems based on long-range ordered ultrathin organic nanomaterials(i.e., below3 nm), which were assembled from stimuli-responsive sequence-controlled biomimetic polymers, remains challenging. Herein,we report the self-assembly of azobenzene-containing amphiphilic ternary alternating peptoids to construct photo-responsive ultrathin peptoids nanoribbons(UTPNRs) with a thickness of ~2.3 nm and the length in several micrometers. The pendants hydrophobic conjugate stacking mechanism explained the formation of one-dimensional ultrathin nanostructures, whose thickness was highly dependent on the length of side groups. The photo-isomerization of azobenzene moiety endowed the aggregates with a reversible morphology transformation from UTPNRs to spherical micelles(46.5 nm), upon the alternative irradiation with ultraviolet and visible light. Donor of 4-(2-hydroxyethylamino)-7-nitro-2,1,3-benzoxadiazole(NBD) and acceptor of rhodamine B(RB) were introduced onto the hydrophobic and hydrophilic regions, respectively, to generate photocontrollable artificial light-harvesting systems. Compared with the spheres-based systems, the obtained NBD-UTPNRs@RB composite proved a higher energy transfer efficiency(90.6%) and a lower requirement of RB acceptors in water. A proof-ofconcept use as fluorescent writable ink demonstrated the potential of UTPNRs on information encryption.
