N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

High-efficiency sodium storage of Co_(0.85)Se/WSe_(2) encapsulated in N-doped carbon polyhedron via vacancy and heterojunction engineering

With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.

Preparation and characterization of visible-light-active nitrogen-doped TiO_2 photocatalyst

A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO_4)_2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wavelength. The crystal structure of anatase was characterized by XRD. The structure analysis result of X-ray fluorescence(XRF) shows that doped-nitrogen was presented in the sample. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants. The photocatalytic activities of samples were increasing gradually with calcination temperature from 400℃ to 700℃ under UV irradiation. It can be seen that the degradation of methyl orange follows zero-order kinetics. However, the calcination temperatures have no significant influence on the degradation of phenol under sunlight. The N-doped catalyst shows higher activity than the bare one under solar irradiation.

Photocatalytic Activity of N-doped TiO2 Photocatalysts Prepared from the Molecular Precursor （NH4）2TiO（C2O4）2

We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO2 photocatalysts calcined below 700 ℃ are the pure anatase phase but that calcined at 700 ℃ is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO2 which leads to the narrowing of bad gap of pure anatase N-TiO2. Among all photocatalysts, N-TiO2 photocatalysts calcined at 600 and 400 ℃ exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO2 photocatalyst calcined at 700 ℃ exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.

Designing N-doped graphene/ReSe_(2)/Ti_(3)C_(2) MXene heterostructure frameworks as promising anodes for high-rate potassium-ion batteries

Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.

In-situ structural evolution analysis of Zr-doped Na_(3)V_(2)(PO_(4))_(2)F_(3) coated by N-doped carbon layer as high-performance cathode for sodium-ion batteries

With great superiorities in energy density,rate capability and structural stability,Na_(3)V_(2)(PO_(4))_(2) F_(3)(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism.Herein,a series of Zr-doped NVPF coated by N-doped carbon layer(~5 nm in thickness,homogenously)materials are fabricated by a sol-gel method,and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity,respectively.Specifically,among all samples of Na_(3) V_(2-x)Zr_(x)(PO_(4))_(2) F_(3)/NC(NVPF-Zr-x/NC,x=0,0.01,0.02,0.05,and 0.1),the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities(119.2 mAh g^(-1) at0.5 C),superior rate capability(98.1 mA h g^(-1) at 20 C)and excellent cycling performance.The structural evolution of NVPF-Zr-0.02/NC electrode,in-situ monitored by X-ray diffractometer,follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes,not just a solid-solutionreaction one.Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity(99.8 mA h g^(-1) at 0.5 C),high out-put voltage(3.5 V)and good cycling stability.This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.

N-doped coaxial CNTs@a-Fe_2O_3@C nanofibers as anode material for high performance lithium ion battery

N-doped coaxial CNTs@α-Fe_2O_3@C nanofibers have been successfully synthesized according to a facile solvothermal/hydrothermal method. The obtained CNTs@α-Fe_2O_3@C nanofibers composites exhibited spe- cial three-dimensional （3-D） network structure, which endows they promising candidate for anode ma- terials of lithium ion battery. The coaxial property of CNTs@α-Fe_2O_3@C nanofibers could significantly improve the cycling and rate performance owing to the acceleration of charge/electron transfer, improve- ment of conductivity, maintaining of structural integrity and inhibiting the aggregation. The α-Fe_2O_3 nanoparticles with small size and high percentage of N-doped amount could further improve the elec- trochemical performance. As for the CNTs@α-Fe_2O_3@C nanofibers, the capacity presented a high value of 1255.4 mAh/g at 0.1 C, and retained at 1213.4 mAh/g after 60 cycles. Even at high rate of 5 C, the ca- pacity still exhibited as high as 319 mAh/g. The results indicated that the synthesized N-doped coaxial CNTs@α-Fe_2O_3@C nanofibers exhibited high cvcling and rate oerformance.

Visible Light-Responsive N-Doped TiO_(2) Photocatalysis:Synthesis,Characterizations,and Applications

Photocatalysis based on semiconductors has recently been receiving considerable research interest because of its extensive applications in environmental remediation and renewable energy generation.Various semiconductor-based materials that are vital to solar energy utilization have been extensively investigated,among which titanium oxide(TiO_(2))has attracted considerable attention because of its exceptional physicochemical characteristics.However,the sluggish responsiveness to visible light in the solar spectrum and the inefficient separation of photoinduced electron-hole pairs hamper the practical application of TiO_(2) materials.To overcome the aforementioned serious drawbacks of TiO_(2),numerous strategies,such as doping with foreign atoms,particularly nitrogen(N),have been improved in the past few decades.This review aims to provide a comprehensive update and description of the recent developments of N-doped TiO_(2) materials for visible lightresponsive photocatalysis,such as(1)the preparation of N-doped/co-doped TiO_(2) photocatalysts and(2)mechanistic studies on the reasons for visible light response.Furthermore,the most recent and significant advances in the field of solar energy applications of modified N-doped TiO_(2) are summarized.The analysis indicated the critical need for further development of these types of materials for the solar-to-energy conversion,particularly for water splitting purposes.

Well-dispersed SnO2 nanocrystals on N-doped carbon nanowires as efficient electrocatalysts for carbon dioxide reduction

The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.

Surface regulated Ni nanoparticles on N-doped mesoporous carbon as an efficient electrocatalyst for CO_(2)reduction

Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.

Engineering single-atom Mn on nitrogen-doped carbon to regulate lithium-peroxide reaction kinetics for rechargeable lithium-oxygen batteries

Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.

In-situ preparation of TiO_(2)/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO_(2) reduction performance

Photocatalytic CO_(2)conversion efficiency is hampered by the rapid recombination of photogenerated charge carriers.It is effective to suppress the recombination by constructing cocatalysts on photocatalysts with high-quality interfacial contact.Herein,we develop a novel strategy to in-situ grow ultrathin/V-doped graphene(NG)layer on TiO_(2) hollow spheres(HS) with large area and intimate interfacial contact via a chemical vapor deposition(CVD).The optimized TiO^(2)/NG HS nanocomposite achieves total CO_(2)conversion rates(the sum yield of CO,CH_(3)OH and CH_(4))of 18.11μmol·g^(-1)h^(-1),which is about 4.6 times higher than blank T1O_(2)HS.Experimental results demonstrate that intimate interfacial contact and abundant pyridinic N sites can effectively facilitate photogenerated charge carrier separation and transport,realizing enhanced photocatalytic CO_(2)reduction performance.In addition,this work provides an effective strategy for in-situ construction of graphene-based photocatalysts for highly efficient photocatalytic CO_(2)conversion.

Hierarchical N-doped carbon nanocages/carbon textiles as a flexible O2 electrode for Li–O2 batteries

The conventional Li–O2 battery(LOB)has hardly been considered as a next-generation flexible electronics thus far,since it is bulk,inflexible and limited by the absence of an adjustable cell configuration.Here,we present a flexible Li–O2 cell using N-doped carbon nanocages grown onto the carbon textiles(NCNs/CTs)as a self-standing and binder-free O2 electrode.The highly flexible NCNs/CTs exhibits an excellent mechanic durability,a promising catalytic activity towards the ORR and OER,a considerable cyclability of more than 70 cycles with an overpotential of 0.36 V on the 1 stcycle at a constant current density of 0.2 m A/cm2,a good rate capability,a superior reversibility with formation and decomposition of desired Li2 O2,and a highly electrochemical stability even under stringent bending and twisting conditions.Our work represents a promising progress in the material development and architecture design of O2 electrode for flexible LOBs.

Co_(2)N Nanoparticles Anchored on N-Doped Active Carbon as Catalyst for Oxygen Reduction Reaction in Zinc–Air Battery

The development of efficient catalytic electrode toward oxygen reduction reaction(ORR)is still a great challenge for the wide use of zinc–air batteries.Herein,Co_(2)N nanoparticles(NPs)anchored on N-doped carbon from cattail were verified with excellent catalytic performances for ORR.The onset and half-wave potentials over the optimal catalyst reach to 0.96 V and 0.84 V,respectively.Current retention rates of 96.8%after 22-h test and 98.8%after running 1600 s were obtained in 1 M methanol solution.Density functional theory simulation proposes an apparently increased electronic states of Co_(2)N in N-doped carbon layer close to the Fermi level.Higher charge density,favorable adsorption,and charge transfer of intermediates originate from the coexistence of Co_(2)N NPs and N atoms in carbon skeleton.The superior catalytic activity of composites also was confirmed in zinc–air batteries.This novel catalytic property and controllable preparation approach of Co_(2)Ncarbon composites provide a promising avenue to fabricate metal-containing catalytically active carbon from biomass.

Unraveling the Role of Nitrogen-Doped Carbon Nanowires Incorporated with MnO_(2)Nanosheets as High Performance Cathode for Zinc-Ion Batteries

Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.

SnS_2 nanosheets arrays sandwiched by N-doped carbon and TiO_2 for high-performance Na-ion storage

In this paper, SnS_2 nanosheets arrays sandwiched by porous N-doped carbon and TiO_2(TiO_2@SnS_2@N-C) on flexible carbon cloth are prepared and tested as a free-standing anode for high-performance sodium ion batteries. The as-obtained TiO_2@SnS_2@N-C composite delivers a remarkable capacity performance(840 mA h g^(-1) at a current density of 200 mA g^(-1)), excellent rate capability and long-cycling life stability(293 mA h g^(-1) at 1 A g^(-1) after 600 cycles). The excellent electrochemical performance can be attributed to the synergistic effect of each component of the unique hybrid structure, in which the SnS_2 nanosheets with open framworks offer high capacity, while the porous N-doped carbon nanoplates arrays on flexible carbon cloth are able to improve the conductivity and the TiO_2 passivation layer can keep the structure integrity of SnS_2 nanosheets.

Effects of N-doping concentration on the electronic structure and optical properties of N-doped β-Ga_2O_3

The electronic structures and the optical properties of N-doped β-Ga2O3 with different N-doping concentrations are studied using the first-principles method.We find that the N substituting O（1） atom is the most stable structure for the smallest formation energy.After N-doping,the charge density distribution significantly changes,and the acceptor impurity level is introduced above the valence band and intersects with the Fermi level.The impurity absorption edges appear to shift toward longer wavelengths with an increase in N-doping concentration.The complex refractive index shows metallic characteristics in the N-doped β-Ga2O3.

“H_(2)-free” demethoxylation of guaiacol in subcritical water using Pt supported on N-doped carbon catalysts:A cost-effective strategy for biomass upgrading

"H_(2)-free" HDO is a revolutionary route to circumvent the limitations of H_(2)-fed HDO reactors for biomass upgrading.This work demonstrates the viability of this economically appealing route when an adequate catalyst is implemented.Herein,we have developed a new family of Pt catalysts supported on N-doped activated carbons for the H_(2)-free HDO process of guaiacol.Several N-donors have been used to tune the catalyst’s structural and electronic properties.As a general trend,the N-promoted samples are more selective towards oxygen-depleted products.The best performing material,namely Pt/PANI-AC reached outstanding guaiacol conversion values-ca.75% at 300℃ while displaying reasonable stability for multiple recycling operations.The advanced performance is ascribed to the modified electronic and acid-base properties which favor guaiacol activation and C-O cleavage,as well as the excellent dispersion of the Pt nano particles.

A Density Functional Study of N-Doped TiO_2 Anatase Cluster

A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations confirmed that the most structures in substitutional model consist of a two-coordinate bridge structure and a three-coordinate hollow structure. The calculated results can well explain the red shift in N-doped TiO2 observed in experiments. The study provides an illustration for the N-doped anatase from the viewpoint of chemical bonding theory.

ZrO_(2) and Nitrogen-doped Carbon Co-coated LiFePO_(4) Cathode with Improved Cycling Stability and Rate Performance for Lithium Batteries

LiFePO_(4)cathode was successfully co-coated by ZrO_(2)and N-doped carbon layer based on the coprecipitation of Zr species and polydopamine on the LiFePO_(4)surfaces.The mutual promotion between the hydrolyzation of ZrO_(2)precursor and the self-polymerization of dopamine was realized in the one-step synthesis.After being used in the coin battery as cathode material,the ZrO_(2)and N-doped carbon co-coated LiFePO_(4)displayed improved cycling stability(97.0%retention at 0.2 C after 200 cycles)and enhanced rate performance(130.7 mAh·g^(−1) at 1 C)due to its higher electrochemical reactivity and reversibility compared with those of commercial LiFePO_(4).