Photocatalytic water splitting by semiconductors is a promising technology to produce clean H_(2) fuel,but the efficiency is restrained seriously by the high overpotential of the H_(2)-evolution reaction together with...Photocatalytic water splitting by semiconductors is a promising technology to produce clean H_(2) fuel,but the efficiency is restrained seriously by the high overpotential of the H_(2)-evolution reaction together with the high recombination rate of photoinduced charges.To enhance H_(2) production,it is highly desirable yet challenging to explore an efficient reductive cocatalyst and place it precisely on the right sites of the photocatalyst surface to work the proton reduction reaction exclusively.Herein,the metalloid NixP cocatalyst is exactly positioned on the Z-scheme Cd_(0.5)Zn_(0.5)S/NiTiO_(3)(CZS/NTO)heterostructure through a facile photodeposition strategy,which renders the cocatalyst form solely at the electron-collecting locations.It is revealed that the directional transfer of photoexcited electrons from Cd_(0.5)Zn_(0.5)S to Ni_(x)P suppresses the quenching of charge carriers.Under visible light,the CZS/NTO hybrid loaded with the Ni_(x)P cocatalyst exhibits an optimal H_(2) yield rate of 1103μmol h^(-1)(i.e.,27.57 mmol h^(-1)g^(-1)),which is about twofold of pristine CZS/NTO and comparable to the counterpart deposited with the Pt cocatalyst.Besides,the high apparent quantum yield(AQY)of 56%is reached at 400 nm.Further,the mechanisms of the cocatalyst formation and the H2 generation reaction are discussed in detail.展开更多
The strong chiroptical effect is highly desirable and has a wide range of applications in biosensing, chiral catalysis,polarization tuning, and chiral photo detection. In this work, we find a simple method to enhance ...The strong chiroptical effect is highly desirable and has a wide range of applications in biosensing, chiral catalysis,polarization tuning, and chiral photo detection. In this work, we find a simple method to enhance the reflection circular dichroism(CDR) by placing the planar anisotropic chiral metamaterials(i.e., Z-shaped PACMs) on the interface of two media(i.e., Z-PCMI) with a large refractive index difference. The maximum reflection CDR from the complex system can reach about 0.840 when the refractive index is set as ntop = 4.0 and nbottom = 1.49, which is approximately three times larger than that of placing the Z-shaped PACMs directly on the substrate(i.e., Z-PCMS). While the minimum reflection CDR is 0.157 when the refractive index is set as ntop = 1.0 and nbottom = 1.49. So we can get a large available range of reflection CDR from -0.840 to -0.157. Meanwhile, the transmission CDT remains unchanged with the refractive index ntop increment. Our in-depth research indicates that the large reflection CDR is derived from the difference of non-conversion components of the planar anisotropic chiral metamaterials’ reflection matrices. In short, we provide a simple and practical method to enhance the chiroptical effect by changing the refractive index difference between two media without having to design a complex chiral structure.展开更多
High performance optical diode-like devices are highly desired in future practical nano-photonic devices with strong directional selectivity.We demonstrate a kind of giant broadband reciprocity optical diode-like devi...High performance optical diode-like devices are highly desired in future practical nano-photonic devices with strong directional selectivity.We demonstrate a kind of giant broadband reciprocity optical diode-like devices by simultaneously using the directional Mie scattering effect and the asymmetric grating diffraction effect.The maximum asymmetric subtraction and the asymmetric transmission ratio can reach nearly 100%and 40dB at specified wavelength,respectively.In a wide waveband from 500nm to 800nm,the asymmetric subtraction and the ratio keep larger than 80%and 3.5 dB,respectively,even under oblique incidence.To the best of our knowledge,this is the best one-way-transmission effect observed in the reciprocity optical diode-like devices.In addition,we further demonstrate that this one-way-transmission effect can bring an effective absorption enhancement on gold films.The giant,broadband and angle-insensitive one-way-transmission effect demonstrated here is far beyond the well-known anti-reflection effect in the light-trapping devices and will bring new design philosophy for nano-photonic devices.展开更多
Poly(heptazine imide)(PHI),a semicrystalline version of carbon nitride photocatalyst based on heptazine units,has gained significant attention for solar H_(2)production benefiting from its advantages including molecul...Poly(heptazine imide)(PHI),a semicrystalline version of carbon nitride photocatalyst based on heptazine units,has gained significant attention for solar H_(2)production benefiting from its advantages including molecular synthetic versatility,excellent physicochemical stability and suitable energy band structure to capture visible photons.Typically,PHI is obtained in saltmelt synthesis in the presence of alkali metal chlorides.Herein,we examined the role of binary alkali metal bromides(LiBr/NaBr)with diverse compositions and melting points to rationally modulate the polymerization process,structure,and properties of PHI.Solid characterizations revealed that semicrystalline PHI with a condensedπ-conjugated system and rapid charge separation rates were obtained in the presence of LiBr/NaBr.Accordingly,the apparent quantum yield of hydrogen using the optimized PHI reaches up to 62.3%at 420 nm.The density functional theory calculation shows that the dehydrogenation of the ethylene glycol has a lower energy barrier than the dehydrogenation of the other alcohols from the thermodynamic point of view.This study holds great promise for rational modulation of the structure and properties of conjugated polymeric materials.展开更多
Highly crystalline carbon nitride polymers have shown great opportunities in overall water photosplitting;however,their mission in light-driven CO_(2)conversion remains to be explored.In this work,crystalline carbon n...Highly crystalline carbon nitride polymers have shown great opportunities in overall water photosplitting;however,their mission in light-driven CO_(2)conversion remains to be explored.In this work,crystalline carbon nitride(CCN)nanosheets of poly triazine imide(PTI)embedded with melon domains are fabricated by KCl/LiCl-mediated polycondensation of dicyandiamide,the surface of which is subsequently deposited with ultrafine WO_(3)nanoparticles to construct the CCN/WO_(3)heterostructure with a S-scheme interface.Systematic characterizations have been conducted to reveal the compositions and structures of the S-scheme CCN/WO_(3)hybrid,featuring strengthened optical capture,enhanced CO_(2)adsorption and activation,attractive textural properties,as well as spatial separation and directed movement of light-triggered charge carriers.Under mild conditions,the CCN/WO_(3)catalyst with optimized composition displays a high photocatalytic activity for reducing CO_(2)to CO in a rate of 23.0μmol/hr(i.e.,2300μmol/(hr·g)),which is about 7-fold that of pristine CCN,along with a high CO selectivity of 90.6%against H2formation.Moreover,it also manifests high stability and fine reusability for the CO_(2)conversion reaction.The CO_(2)adsorption and conversion processes on the catalyst are monitored by in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),identifying the crucial intermediates of CO_(2)^(*)-,COOH^(*)and CO^(*),which integrated with the results of performance evaluation proposes the possible CO_(2)reduction mechanism.展开更多
Polymeric carbon nitride has been widely developed as a promising photocatalyst for solar hydrogen production via photocatalytic water splitting.However,pristine carbon nitride prepared by traditional solid-state poly...Polymeric carbon nitride has been widely developed as a promising photocatalyst for solar hydrogen production via photocatalytic water splitting.However,pristine carbon nitride prepared by traditional solid-state polymerization usually encounters issues such as rapid carrier recombination and insufficient absorption of visible light below 460 nm.Herein,poly(heptazine imide)with a distinctive nanoplate structure was synthesized in a binary molten salt of NaCl–CaCl_(2).The salt template allows the formation of the thin nanoplate structure,which promotes the charge separation and migration.Besides,the intercalation of Ca^(2+)ions between the conjugated layers endows the activation of n–π*electron transition due to the distortion of in-plane heptazine layers.Accordingly,the optimized poly(heptazine imide)nanoplates achieve an apparent quantum efficiency of up to 17.3%at 500 nm for photocatalytic hydrogen production from water.This work shares new idea for rational control of the optical absorption and charge carrier dynamics of poly(heptazine imide).展开更多
Sunlight-induced photocatalytic carbon dioxide(CO_(2))reduction to energy-rich chemicals by metal-free polymeric carbon nitride(CN)semiconductor is a promising tactic for sustained solar fuel production.However,the re...Sunlight-induced photocatalytic carbon dioxide(CO_(2))reduction to energy-rich chemicals by metal-free polymeric carbon nitride(CN)semiconductor is a promising tactic for sustained solar fuel production.However,the reaction efficiency of CO_(2)photoreduction is restrained seriously by the rapid recombination of photogenerated carriers on CN polymer.Herein,we incorporate 2-aminopyridine molecule with strong electron-withdrawing group into the skeleton edge of CN layers through a facile one-pot thermal polymerization strategy using urea as the precursor,which renders a modified carbon nitride(ACN)with extended optical harvesting,abundant nitrogen defects and ultrathin nanosheet structure.Consequently,the ACN photocatalyst with desirable structural features attains enhanced separation and migration of photoexcited charge carriers.Under visible light irradiation with Co(bpy)^(2+)_(3)as a cocatalyst,the optimized ACN sample manifests a high CO_(2)deoxygnative reduction activity and high sta-bility,providing a CO yielding rate of 17μmol h^(-1),which is significantly higher than that of pristine CN.The key intermediates engaged in CO_(2)photoreduction reaction are determined by the in situ diffuse reflectance infrared Fourier transform spectroscopy,which sponsors the construction of the possible photocatalytic CO_(2)reduction mechanism on ACN nanosheets.展开更多
Silver nanoparticles（Ag NPs） were successfully assembled in porous anodic alumina（AAO） templates via a green silver mirror reaction.The Ag NPs/AAO composite templates then were characterized by field emission scan...Silver nanoparticles（Ag NPs） were successfully assembled in porous anodic alumina（AAO） templates via a green silver mirror reaction.The Ag NPs/AAO composite templates then were characterized by field emission scanning electron microscopy（FESEM）,energy-dispersive X-ray microanalysis（EDX）,and X-ray diffraction（XRD）.Furthermore,the photoluminescence（PL） properties were also investigated.Compared with the blank AAO,the PL intensity of Ag NPs/AAO templates are enhanced and the maximum enhancement is 2.58 times.Based on the local electric field enhancement effect,the theoretical values were also deduced,which are basically coincident with the experimental.展开更多
基金supported by the National Key R&D Program of China(2021YFA1502100 and 2022YFE0114800)the National Natural Science Foundation of China(22372035,22302039 and 22311540011).
文摘Photocatalytic water splitting by semiconductors is a promising technology to produce clean H_(2) fuel,but the efficiency is restrained seriously by the high overpotential of the H_(2)-evolution reaction together with the high recombination rate of photoinduced charges.To enhance H_(2) production,it is highly desirable yet challenging to explore an efficient reductive cocatalyst and place it precisely on the right sites of the photocatalyst surface to work the proton reduction reaction exclusively.Herein,the metalloid NixP cocatalyst is exactly positioned on the Z-scheme Cd_(0.5)Zn_(0.5)S/NiTiO_(3)(CZS/NTO)heterostructure through a facile photodeposition strategy,which renders the cocatalyst form solely at the electron-collecting locations.It is revealed that the directional transfer of photoexcited electrons from Cd_(0.5)Zn_(0.5)S to Ni_(x)P suppresses the quenching of charge carriers.Under visible light,the CZS/NTO hybrid loaded with the Ni_(x)P cocatalyst exhibits an optimal H_(2) yield rate of 1103μmol h^(-1)(i.e.,27.57 mmol h^(-1)g^(-1)),which is about twofold of pristine CZS/NTO and comparable to the counterpart deposited with the Pt cocatalyst.Besides,the high apparent quantum yield(AQY)of 56%is reached at 400 nm.Further,the mechanisms of the cocatalyst formation and the H2 generation reaction are discussed in detail.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11604227).
文摘The strong chiroptical effect is highly desirable and has a wide range of applications in biosensing, chiral catalysis,polarization tuning, and chiral photo detection. In this work, we find a simple method to enhance the reflection circular dichroism(CDR) by placing the planar anisotropic chiral metamaterials(i.e., Z-shaped PACMs) on the interface of two media(i.e., Z-PCMI) with a large refractive index difference. The maximum reflection CDR from the complex system can reach about 0.840 when the refractive index is set as ntop = 4.0 and nbottom = 1.49, which is approximately three times larger than that of placing the Z-shaped PACMs directly on the substrate(i.e., Z-PCMS). While the minimum reflection CDR is 0.157 when the refractive index is set as ntop = 1.0 and nbottom = 1.49. So we can get a large available range of reflection CDR from -0.840 to -0.157. Meanwhile, the transmission CDT remains unchanged with the refractive index ntop increment. Our in-depth research indicates that the large reflection CDR is derived from the difference of non-conversion components of the planar anisotropic chiral metamaterials’ reflection matrices. In short, we provide a simple and practical method to enhance the chiroptical effect by changing the refractive index difference between two media without having to design a complex chiral structure.
基金Supported by the National Natural Science Foundation of China under Grant No.11604227。
文摘High performance optical diode-like devices are highly desired in future practical nano-photonic devices with strong directional selectivity.We demonstrate a kind of giant broadband reciprocity optical diode-like devices by simultaneously using the directional Mie scattering effect and the asymmetric grating diffraction effect.The maximum asymmetric subtraction and the asymmetric transmission ratio can reach nearly 100%and 40dB at specified wavelength,respectively.In a wide waveband from 500nm to 800nm,the asymmetric subtraction and the ratio keep larger than 80%and 3.5 dB,respectively,even under oblique incidence.To the best of our knowledge,this is the best one-way-transmission effect observed in the reciprocity optical diode-like devices.In addition,we further demonstrate that this one-way-transmission effect can bring an effective absorption enhancement on gold films.The giant,broadband and angle-insensitive one-way-transmission effect demonstrated here is far beyond the well-known anti-reflection effect in the light-trapping devices and will bring new design philosophy for nano-photonic devices.
基金financially supported by the National Key R&D Program of China (2021YFA1502100)the National Natural Science Foundation of China (22172029 and 22002016)the Science Foundation of Fujian Province (2022L3084)。
基金National Key R&D Program of China,Grant/Award Number:2021YFA1502100National Natural Science Foundation of China,Grant/Award Number:22172029Science Foundation of the Fujian Province,Grant/Award Number:2022L3084。
文摘Poly(heptazine imide)(PHI),a semicrystalline version of carbon nitride photocatalyst based on heptazine units,has gained significant attention for solar H_(2)production benefiting from its advantages including molecular synthetic versatility,excellent physicochemical stability and suitable energy band structure to capture visible photons.Typically,PHI is obtained in saltmelt synthesis in the presence of alkali metal chlorides.Herein,we examined the role of binary alkali metal bromides(LiBr/NaBr)with diverse compositions and melting points to rationally modulate the polymerization process,structure,and properties of PHI.Solid characterizations revealed that semicrystalline PHI with a condensedπ-conjugated system and rapid charge separation rates were obtained in the presence of LiBr/NaBr.Accordingly,the apparent quantum yield of hydrogen using the optimized PHI reaches up to 62.3%at 420 nm.The density functional theory calculation shows that the dehydrogenation of the ethylene glycol has a lower energy barrier than the dehydrogenation of the other alcohols from the thermodynamic point of view.This study holds great promise for rational modulation of the structure and properties of conjugated polymeric materials.
基金supported by the National Key R&D Program of China(Nos.2021YFA1502100 and 2022YFE0114800)the National Natural Science Foundation of China(Nos.22311540011 and 21973014)。
文摘Highly crystalline carbon nitride polymers have shown great opportunities in overall water photosplitting;however,their mission in light-driven CO_(2)conversion remains to be explored.In this work,crystalline carbon nitride(CCN)nanosheets of poly triazine imide(PTI)embedded with melon domains are fabricated by KCl/LiCl-mediated polycondensation of dicyandiamide,the surface of which is subsequently deposited with ultrafine WO_(3)nanoparticles to construct the CCN/WO_(3)heterostructure with a S-scheme interface.Systematic characterizations have been conducted to reveal the compositions and structures of the S-scheme CCN/WO_(3)hybrid,featuring strengthened optical capture,enhanced CO_(2)adsorption and activation,attractive textural properties,as well as spatial separation and directed movement of light-triggered charge carriers.Under mild conditions,the CCN/WO_(3)catalyst with optimized composition displays a high photocatalytic activity for reducing CO_(2)to CO in a rate of 23.0μmol/hr(i.e.,2300μmol/(hr·g)),which is about 7-fold that of pristine CCN,along with a high CO selectivity of 90.6%against H2formation.Moreover,it also manifests high stability and fine reusability for the CO_(2)conversion reaction.The CO_(2)adsorption and conversion processes on the catalyst are monitored by in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),identifying the crucial intermediates of CO_(2)^(*)-,COOH^(*)and CO^(*),which integrated with the results of performance evaluation proposes the possible CO_(2)reduction mechanism.
基金financially supported by the National Key R&D Program of China(2021YFA1502100)the National Natural Science Foundation of China(22032002,22172029,22311540011,22202045,22002016,and U1905214)the 111 Project(D16008)。
文摘Polymeric carbon nitride has been widely developed as a promising photocatalyst for solar hydrogen production via photocatalytic water splitting.However,pristine carbon nitride prepared by traditional solid-state polymerization usually encounters issues such as rapid carrier recombination and insufficient absorption of visible light below 460 nm.Herein,poly(heptazine imide)with a distinctive nanoplate structure was synthesized in a binary molten salt of NaCl–CaCl_(2).The salt template allows the formation of the thin nanoplate structure,which promotes the charge separation and migration.Besides,the intercalation of Ca^(2+)ions between the conjugated layers endows the activation of n–π*electron transition due to the distortion of in-plane heptazine layers.Accordingly,the optimized poly(heptazine imide)nanoplates achieve an apparent quantum efficiency of up to 17.3%at 500 nm for photocatalytic hydrogen production from water.This work shares new idea for rational control of the optical absorption and charge carrier dynamics of poly(heptazine imide).
基金supported by the National Key R&D Program of China(2021YFA1502100 and 2022YFE0114800)the National Natural Science Foundation of China(22372035,22302039 and 22311540011).
文摘Sunlight-induced photocatalytic carbon dioxide(CO_(2))reduction to energy-rich chemicals by metal-free polymeric carbon nitride(CN)semiconductor is a promising tactic for sustained solar fuel production.However,the reaction efficiency of CO_(2)photoreduction is restrained seriously by the rapid recombination of photogenerated carriers on CN polymer.Herein,we incorporate 2-aminopyridine molecule with strong electron-withdrawing group into the skeleton edge of CN layers through a facile one-pot thermal polymerization strategy using urea as the precursor,which renders a modified carbon nitride(ACN)with extended optical harvesting,abundant nitrogen defects and ultrathin nanosheet structure.Consequently,the ACN photocatalyst with desirable structural features attains enhanced separation and migration of photoexcited charge carriers.Under visible light irradiation with Co(bpy)^(2+)_(3)as a cocatalyst,the optimized ACN sample manifests a high CO_(2)deoxygnative reduction activity and high sta-bility,providing a CO yielding rate of 17μmol h^(-1),which is significantly higher than that of pristine CN.The key intermediates engaged in CO_(2)photoreduction reaction are determined by the in situ diffuse reflectance infrared Fourier transform spectroscopy,which sponsors the construction of the possible photocatalytic CO_(2)reduction mechanism on ACN nanosheets.
基金the National Natural Science Foundation of China (Grand Nos.60878031,J0830308)the National Basic Research Programme of China (Grant No.2006CB302902)the Natural Science Foundation of Chaohu College (Grant No.XLY-200813)
文摘Silver nanoparticles（Ag NPs） were successfully assembled in porous anodic alumina（AAO） templates via a green silver mirror reaction.The Ag NPs/AAO composite templates then were characterized by field emission scanning electron microscopy（FESEM）,energy-dispersive X-ray microanalysis（EDX）,and X-ray diffraction（XRD）.Furthermore,the photoluminescence（PL） properties were also investigated.Compared with the blank AAO,the PL intensity of Ag NPs/AAO templates are enhanced and the maximum enhancement is 2.58 times.Based on the local electric field enhancement effect,the theoretical values were also deduced,which are basically coincident with the experimental.
