Enhanced conversion of CO2 into C2H4 on single atom Cu-anchored graphitic carbon nitride: Synergistic diatomic active sites interaction.

Single atom metal-nitrogen-carbon materials have emerged as remarkably potent catalysts, demonstrating unprecedented potential for the photo-driven reduction of CO2. Herein, a unique Cu@g-C3N5 catalyst obtained by cooperation of single atom Cu and nitrogen-rich g-C3N5 is proposed. The particular CuN diatomic active sites (DAS) in Cu@g-C3N5 contribute to the formation of highly stable CuOCN adsorption, a key configuration for CO2 activation and CC coupling. The synergistic diatomic active sites interaction is found responsible for the efficient photoreduction of CO2 to C2H4 which has been demonstrated in our Gibbs free energy calculation and COHP analysis. The CO2 activation mechanism was studied, the charge density difference and DOS analysis show that the low oxidation state Cu atom significantly affects the electronic structure of g-C3N5 and then enhance the catalytic activity of CO2 hydrogenation.

Efficient photoreduction of carbon dioxide to ethanol using diatomic nitrogen-doped black phosphorus.

Successful conversion of CO2 into C2 products requires the development of new catalysts that overcome the difficulties in efficient light harvesting and CO-CO coupling. Herein, density functional theory (DFT) is used to assess the photoreduction properties of nitrogen-doped black phosphorus. The geometric structure, redox potential, first step of hydrogenation activation, CO desorption, and CO-CO coupling are systematically calculated, based on which the diatomic nitrogen-doped black phosphorus (N2@BPV) stands out. The calculated results of the CO2RR pathway demonstrate that N2@BPV has excellent selectivity and high activity for CH3CH2OH production. The results of the time-dependent ab initio nonadiabatic molecular dynamics simulation show that the diatomic N active sites of N2@BPV facilitate charge separation and inhibit electron-hole recombination. In addition, the activation mechanism of CO2 is studied. The main reason for CO2 activation is attributed to the imbalance in electron transfer that destroys the symmetry of CO2. We expect that our study will offer some theoretical guidance in CO2 conversion.

Enhancing photocatalytic overall water-splitting performance on dual-active-sites of the Co-P@MoS2 catalysts: a DFT study.

The rational construction of photocatalysts possesses tremendous potential to solve the energy crisis and environmental pollution; however, designing a catalyst for solar-driven overall water-splitting remains a great challenge. Herein, we propose a new MoS2-based photocatalyst (Co-P@MoS2), which skillfully uses the cobalt (Co) atom to stimulate in-plane S atoms and employs the phosphorus (P) atom to stabilize the basal plane by forming the Co-P bands. Using density functional theory (DFT), it was found that oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) can occur at the P site and S2 site of the Co-P@MoS2, respectively, and the dual-active sites successfully makes a delicate balance between the adsorption and dissociation of hydrogen. Furthermore, the improved overall water-splitting performance of Co-P@MoS2 was verified by analyzing the results of the electron structure and the dynamics of photogenerated carries. It was found that the imbalance of electron transfer caused by the introduction of the Co atom was the main contributor to the catalytic activity of Co-P@MoS2. Our study broadens the idea of developing photocatalysts for the overall water-splitting.

NiFe Nanoparticle-Encapsulated Ultrahigh-Oxygen-Doped Carbon Layers as Bifunctional Electrocatalysts for Rechargeable Zn-Air Batteries.

There is an urgent demand for developing highly efficient bifunctional electrocatalysts with excellent stability toward the oxygen evolution and reduction reactions (OER and ORR, respectively) for rechargeable Zn-air batteries (ZABs). In this work, NiFe nanoparticles encapsulated within ultrahigh-oxygen-doped carbon quantum dots (C-NiFe) as bifunctional electrocatalysts are successfully obtained. The accumulation of carbon layers formed by carbon quantum dots results in abundant pore structures and a large specific surface area, which is favorable for improving catalytic active site exposure, ensuring high electronic conductivity and stability simultaneously. The synergistic effect of NiFe nanoparticles enriched the number of active centers and naturally increased the inherent electrocatalytic performance. Benefiting from the above optimization, C-NiFe shows excellent electrochemical activity for both OER and ORR processes (the OER overpotential is only 291 mV to achieve 10 mA cm-2). Furthermore, the C-FeNi catalyst as an air cathode displays an impressive peak power density of 110 mW cm-2, an open-circuit voltage of 1.47 V, and long-term durability over 58 h. The preparation of this bifunctional electrocatalyst provides a design idea for the construction of bimetallic NiFe composites for high-performance Zn-air batteries.

Efficient Removal of Pb(â ¡) by Highly Porous Polymeric Sponges Self-Assembled from a Poly(Amic Acid).

Lead (II) (Pb(II)) is widespread in water and very harmful to creatures, and the efficient removal of it is still challenging. Therefore, we prepared a novel sponge-like polymer-based absorbent (poly(amic acid), PAA sponge) with a highly porous structure using a straightforward polymer self-assembly strategy for the efficient removal of Pb(II). In this study, the effects of the pH, dosage, adsorption time and concentration of Pb(II) on the adsorption behavior of the PAA sponge are investigated, revealing a rapid adsorption process with a removal efficiency up to 89.0% in 2 min. Based on the adsorption thermodynamics, the adsorption capacity increases with the concentration of Pb(II), reaching a maximum adsorption capacity of 609.7 mg g-1 according to the Langmuir simulation fitting. Furthermore, the PAA sponge can be efficiently recycled and the removal efficiency of Pb(II) is still as high as 93% after five adsorption-desorption cycles. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses reveal that the efficient adsorption of Pb(II) by the PAA sponge is mainly due to the strong interaction between nitrogen-containing functional groups and Pb(II), and the coordination of oxygen atoms is also involved. Overall, we propose a polymer self-assembly strategy to easily prepare a PAA sponge for the efficient removal of Pb(II) from water.

Highly porous nitrogen-doped carbon superstructures derived from the intramolecular cyclization-induced crystallization-driven self-assembly of poly(amic acid).

Hierarchically porous carbon nanomaterials have shown significant potential in electrochemical energy storage due to the promoted charge and mass transfer. Herein, a facile template-free method is proposed to prepare nitrogen-doped carbon superstructures (N-CSs) with multi-level pores by pyrolysis of polymeric precursors derived from the intramolecular cyclization-induced crystallization-driven self-assembly (ICI-CDSA) of poly(amic acid) (PAA). The excellent thermal stability of PAA enables the N-CSs to inherit the hierarchical structure of the precursors during pyrolysis, which facilitates the formation of meso- and macropores while the decomposition of the precursors promotes the creation of micropores. Electrochemical tests demonstrate the ultrahigh surface-area-normalized capacitance (76.5 µF cm-2) of the N-CSs facilitated by the hierarchically porous structure, promoting the charge and mass transfer, as well as the high utilization of pyridinic and pyrrolic nitrogen (12.9%) to provide significant pseudocapacitance contribution up to 40.6%. Considering the diversity of monomers of PAA, this ICI-CDSA strategy could be extended to prepare carbon nanomaterials with various morphologies, pore structures and chemical compositions.

First-principles calculations of 0D/2D GQDs-MoS2 mixed van der Waals heterojunctions for photocatalysis: a transition from type I to type II.

The fabrication of type II heterojunctions is an efficient strategy to facilitate charge separation in photocatalysis. Here, mixed dimensional 0D/2D van der Waals (vdW) heterostructures (graphene quantum dots (GQDs)-MoS2) for generating hydrogen from water splitting are investigated based on density functional theory (DFT). The electronic and photocatalytic properties of three heterostructures, namely, C6H6-MoS2, C24H12-MoS2 and C32H14-MoS2 are estimated by analyzing the density of states, charge density difference, work function, Bader charge, absorption spectra and band alignment. The results indicated that the built-in electric fields from GQDs to MoS2 boost charge separation. Meanwhile, all the GQDs-MoS2 exhibit strong absorption in the visible light region. Surprisingly, the transition of heterojunctions from type I to type II is realized by tuning the size of GQDs. In particular, C32H14-MoS2 with enhanced visible-light absorption and an appropriate band edge position, as a type II heterostructure, may be a promising photocatalyst for generating hydrogen from water splitting. Thus, in this work a novel type II 0D/2D nanocomposite as a photocatalyst is constructed that provides a strategy to regulate the type of heterostructure from the perspective of theoretical calculation.

A Photoelectrochemical Platform Based on Polyaniline-Modified Titanium Dioxide Facet Heterostructure.

A photoelectrochemical (PEC) electrode for glucose detection was built based on polyaniline (PANI) modified titanium dioxide heterojunction (FH-TiO2) structures. Ultrathin titanium dioxide (TiO2) nanosheets are assembled onto rutile nanorods (TiO2 NRs). Experiments show that the main exposed faces of these nanosheets are (101) or (111) crystal planes. Proven by theoretical calculation, the bottom of the conduction band (CB) of (111) is 0.15 eV lower than the bottom of the conduction band of (101). Therefore, when the material is excited by light, photogenerated electrons are able to transfer from the conduction band of (101) to the conduction band of (111). PANI was introduced as a medium to effectively conduct photogenerated charges between glucose oxidase and titanium dioxide. A photoelectric detection electrode for glucose was fabricated by loading glucose oxidase onto PANI@FH-TiO2. This electrode showed excellent performance in 0.2-1.0 mM linear range with a sensitivity 15.63 µA mM-1 cm-2 and 1.0-15.0 mM linear range with a sensitivity of 1.42 µA mM-1 cm-2.

Theoretical insights on type I/II photoreactions of potential Zn(II) polypyridyl photosensitizers for two-photon photodynamic therapy.

Large two-photon absorption cross-sections are vital to photosensitizers (PSs) in TP-PDT, which can be used to develop in-depth treatment for diseased cells and minimize the harm to surrounding cells. Here, we conduct a study about photophysical properties of one Ru(II) polypyridyl complex and two designed Zn(II) polypyridyl complexes by means of DFT and TD-DFT methods. The main results are as follows: firstly, the two-photon absorption spectrum of two designed complexes Zn-OMe and Zn-OCOOCH3 are all within the phototherapeutic window (550-900 nm). Secondly, large SOC values and small energy gaps ΔES-T of these complexes guarantee the efficiency of ISC process. Thirdly, their T1 energy is greater than that required for generating 1O2 (0.98 eV) via Type II photoreaction. In addition, the calculated results of vertical electron affinities (VEA) and vertical ionization potentials (VIP) show that these complexes are able to form superoxide ions O2(-) via Type I photoreaction. Specifically, both of two designed Zn-centric complexes have larger TPA cross-sections than that of Ru-centric complex. In a word, we are pleased to report two potential photosensitizers with excellent performance and reasonable price for Type I/II photoreactions. We expect our study will offer some theoretical guidance and help in TP-PDT.

Sandwich Photothermal Membrane with Confined Hierarchical Carbon Cells Enabling High-Efficiency Solar Steam Generation.

Solar-driven vaporization is a sustainable solution to water and energy scarcity. However, most of the present evaporators are still suffering from inefficient utilization of converted thermal energy. Herein, a universal sandwich membrane strategy is demonstrated by confining the hierarchical porous carbon cells in two energy barriers to obtain a high-efficiency evaporator with a rapid water evaporation rate of 1.87 kg m-2 h-1 under 1 sun illumination, which is among the highest performance for carbon-based and wood-based evaporators. The significantly enhanced evaporation rate is mainly attributed to the inherently optimized porous evaporation mode derived from the hierarchical hollow structures of pollen carbon cells, and the synergistically regulated water transporting and thermal management performance of the sandwich membrane. Moreover, the constructed sandwich membrane also exhibits excellent self-regenerating performance in simulated seawater and high salinity water. The developed device can maintain an average evaporation rate of 4.3 L m-2 day-1 in a 25 day consecutive outdoor test.

Hierarchical structure N, O-co-doped porous carbon/carbon nanotube composite derived from coal for supercapacitors and CO2 capture.

The energy and environmental crises have forced us to search for a new green energy source and develop energy storage and environmental restoration technologies. Fabrication of carbon functional materials derived from coal has attracted increasing attention in the energy storage and gas adsorption fields. In this study, an N, O-co-doped porous carbon/carbon nanotube composite was prepared by functionalizing coal-based porous carbon with carbon nanotubes (CNTs) and ionic liquid via annealing. The resulting material not only inherited the morphology of CNTs and porous carbon, but also developed a three dimensional (3D) hierarchical porous structure with numerous heteroatom groups. The N, O co-doped porous carbon/CNT composite (N, O-PC-CNTs) showed a surface area of 2164 m2 g-1, and a high level of N/O dopants (8.0 and 3.0 at%, respectively). Benefiting from such merits, N, O-PC-CNTs exhibited a rather high specific capacitance of 287 F g-1 at a current density of 0.2 A g-1 and a high rate capability (70% and 64% capacitance retention at 10 and 50 A g-1, respectively) in a three electrode system. Furthermore, an N, O-PC-CNT symmetrical supercapacitor showed a high cycling stability with 95% capacitance retention after 20 000 cycles at 20 A g-1 and an energy density of 4.5 W h kg-1 at a power density of 12.5 kW kg-1 in 6 mol L-1 KOH electrolyte. As a CO2 adsorbent, N, O-PC-CNTs exhibited a high CO2 uptake of 5.7 and 3.7 mmol g-1 at 1 bar at 273 and 298 K, respectively. Moreover, N, O-PC-CNTs showed cycling stability with 94% retention of the initial CO2 adsorption capacity at 298 K over 10 cycles. This report introduces a strategy to design a coal based porous carbon composite for use in efficient supercapacitor electrodes and CO2 adsorbents.

Theoretical insight into the photophysical properties of long-lifetime Ir(iii) and Rh(iii) complexes for two-photon photodynamic therapy.

Two-photon photodynamic therapy (TP-PDT) plays crucial roles in curing tumors because it involves deep penetration of drugs into the tissue and has minimal damage to the surrounding cells. Our theoretical study was aimed at providing fresh insights into photosensitizers, such as [Ir(N^C)2(N^N)]+ (N^C = 2-phenylpyridine, N^N = bis-benzimidazole) and [Rh(N^C)2(N^N)]+, to treat cancer via the TP-PDT route. To better understand the properties of the complexes [Ir(N^C)2(N^N)]+ and [Rh(N^C)2(N^N)]+, the one-photon and two-photon absorption electronic spectra, energy gap (ΔES-T), strength of two-photon absorption cross-section (δ), spin-orbit matrix element (S1|HSO|Tj), and phosphorescence lifetimes (τ) were calculated by DFT and TD-DFT. The calculation results suggested that both complexes met the criteria (i.e. an efficient ISC process, enough energy to produce 1O2 and phototherapeutic window of the absorption wavelength) of photosensitizers; importantly, the designed complex [Rh(N^C)2(N^N)]+ had better performance than [Ir(N^C)2(N^N)]+, especially in the long-lived triplet excited state. It is expected that our research can make quite a few contributions to the development of photosensitizers and establish some guidelines for experiments based on TP-PDT.

Simultaneous Electrochemical Detection of Nitrite and Hydrogen Peroxide Based on 3D Au-rGO/FTO Obtained Through a One-Step Synthesis.

In this paper, Au and reduced graphene oxide (rGO) were successively deposited on fluorine-doped SnO2 transparent conductive glass (FTO, 1 × 2 cm) via a facile and one-step electrodeposition method to form a clean interface and construct a three-dimensional network structure for the simultaneous detection of nitrite and hydrogen peroxide (H2O2). For nitrite detection, 3D Au-rGO/FTO displayed a sensitivity of 419 µA mM-1 cm-2 and a linear range from 0.0299 to 5.74 mM, while for the detection of H2O2, the sensitivity was 236 µA mM-1 cm-2 and a range from 0.179 to 10.5 mM. The combined results from scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction measurements (XRD) and electrochemical tests demonstrated that the properties of 3D Au-rGO/FTO were attributabled to the conductive network consisting of rGO and the good dispersion of Au nanoparticles (AuNPs) which can provide better electrochemical properties than other metal compounds, such as a larger electroactive surface area, more active sites, and a bigger catalytic rate constant.

Theoretical study on photophysical properties of three high water solubility polypyridyl complexes for two-photon photodynamic therapy.

Two-photon photodynamic therapy (TP-PDT) is a very promising treatment that has drawn much attention in recent years due to its ability to penetrate deeper into tissues and minimize the damage to normal cells. Here, the properties of three highly water soluble Ru(ii) and Zn(ii) polypyridyl complexes as photosensitizers (PSs) were examined, including the one-photon and two-photon absorption (OPA and TPA) spectra, singlet-triplet energy gap (ΔH-L), TPA cross-section and spin-orbit coupling constant via Density Function Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT). Their potential therapeutic use as photosensitizers in TP-PDT is proposed, where the reasoning is as follows: first, they possess strong absorption in the therapeutic window; second, the vertical excitation energy is greater than 0.98 eV, which can generate a singlet oxygen species and the remarkable coupling between the S1 and T1 states. Moreover, the spin-orbit matrix elements are greater than 0.24 cm-1 for Ru-bpy and Zn-tpy, indicating that the intersystem spin crossing processes are efficient. It is expected that these complexes will be applied to PSs in TP-PDT, and we hope this research can serve as a guideline for the development of efficient two-photon PSs.

A theoretical study of a series of water-soluble triphenylamine photosensitizers for two-photon photodynamic therapy.

In this study, the therapeutic activity of a series of water-soluble triphenylamine (TP) photosensitizers (Ps) was explored by using theoretical simulations. The key photophysical parameters which determined the efficiency of Ps, such as absorption electronic spectra, singlet-triplet energy gaps and spin-orbit matrix elements were calculated at density functional theory and its time-dependent extension (DFT, TD-DFT). The calculated results showed that these TP photosensitizers possessed large two-photon absorption cross-section in the near-infrared region (NIR), efficient intersystem crossing (ISC) transition from the first singlet excited state to the low lying triplet excited states and sufficient energy for generating reactive oxygen species (ROS). These suitable features made these TP series holding great promise for applications in two-photon photodynamic therapy (PDT). These TP photosensitizers studied here in principle extended the application range of two-photon PDT in water solution.

Volatile Organic Compound Gas-Sensing Properties of Bimodal Porous α-Fe2O3 with Ultrahigh Sensitivity and Fast Response.

Porous solid with multimodal pore size distribution provides plenty of advantages including large specific surface area and superior mass transportation to achieve high gas-sensing performances. In this study, α-Fe2O3 nanoparticles with bimodal porous structures were prepared successfully through a nanocasting pathway, adopting the bicontinuous 3D cubic symmetry mesoporous silica KIT-6 as the hard template. Its structure and morphology were characterized by X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, and so on. Furthermore, the gas sensor fabricated from this material exhibited excellent gas-sensing performance to several volatile organic compounds (acetone, ethyl acetate, isopropyl alcohol, n-butanol, ethanol, and methanol), such as ultrahigh sensitivity, rapid response speed (less than 10 s) and recovery time, good reproducibility, as well as stability. These would be associated with the desirable pore structure of the material, facilitating the molecules diffusion toward the entire sensing surface, and providing more active sensing sites for analytical gas.

Ordered mesoporous NiFe2O4 with ultrathin framework for low-ppb toluene sensing.

Highly sensitive and selective detection against specific target gases, especially at low-ppb (part per billion) level, remain a great number of challenges in gas sensor applications. In this paper, we first present an ordered mesoporous NiFe2O4 for highly sensitive and selective detection against low-ppb toluene. A series of mesoporous NiFe2O4 materials were synthesized by templating from mesoporous silica KIT-6 and its framework thickness was reduced from 8.5 to 5 nm by varying the pore size of KIT-6 from 9.4 to 5.6 nm, accompanied with the increase of the specific surface area from 134 to 216 m2 g-1. The ordered mesoporous NiFe2O4 with both ultrathin framework of 5 nm and large specific surface area of up to 216 m2 g-1 exhibits a highest response (Rgas/Rair - 1 = 77.3) toward 1,000 ppb toluene at 230 °C and is nearly 7.3 and 76.7 times higher than those for the NiFe2O4 replica with thick framework and its bulk counterpart respectively, which also possesses a quite low limit of detection (<2 ppb), and good selectivity.

3D NiO hollow sphere/reduced graphene oxide composite for high-performance glucose biosensor.

The 3D NiO hollow sphere/reduced graphene oxide (rGO) composite was synthesized according to the coordinating etching and precipitating process by using Cu2O nanosphere/graphene oxide (GO) composite as template. The morphology, structure, and composition of the materials were characterized by SEM, TEM, HRTEM, XPS, and Raman spectra, and the electrochemical properties were studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and amperometry. Moreover, the electrochemical activity of the composite materials with different morphologies were also investigated, which indicating a better combination of the NiO hollow sphere and the rGO. Used as glucose sensing material, the 3D NiO hollow sphere/rGO composite modified electrode exhibits high sensitivity of ~2.04 mA mM-1 cm-2, quick response time of less than 5 s, good stability, selectivity, and reproducibility. Its application for the detection of glucose in human blood serum sample shows acceptable recovery and R.S.D. VALUES: The outstanding glucose sensing performance should be attributed to the unique 3D hierarchical porous superstructure of the composite, especially for its enhanced electron-transfer kinetic properties.

Ordered Large-Pore Mesoporous Cr2O3 with Ultrathin Framework for Formaldehyde Sensing.

A series of ordered mesoporous chromium oxides (Cr2O3) were synthesized by first replicating bicontinuous cubic Ia3d mesoporous silica (KIT-6), then a controlled mesostructural transformation from Ia3d to I4132 symmetry during the replication from KIT-6 to Cr2O3 was achieved by reducing the pore size and interconnectivities of KIT-6, accompanied with an increase in pore size from 3 to 12 nm and a decrease in framework thickness from 8.6 to 5 nm of the resultant Cr2O3 replicas. The gas-sensing behavior of the Cr2O3 replicas toward formaldehyde (HCHO) was systematically investigated. Ordered mesoporous Cr2O3 with both large accessible pores (12 nm) and an ultrathin framework (5 nm) exhibits the best sensing performance, with a response (Rgas/Rair = 119) toward 9 ppm of HCHO 4.4 times higher than that (Rgas/Rair = 27) of its counterpart with small pores and a thick framework. Moreover, it possesses excellent selectivity for detecting HCHO over other interference gases such as CO, benzene, toluene, p-xylene, NH3, H2S, and moisture. The significantly enhanced sensing performance of ordered large-pore mesoporous Cr2O3 with ultrathin framework suggests its great potential for the selective detection of HCHO.

Hierarchical NiCo2O4 Hollow Sphere as a Peroxidase Mimetic for Colorimetric Detection of H2O2 and Glucose.

In this work, the hierarchical NiCo2O4 hollow sphere synthesized via a "coordinating etching and precipitating" process was demonstrated to exhibit intrinsic peroxidase-like activity. The peroxidase-like activity of NiCo2O4, NiO, and Co3O4 hollow spheres were comparatively studied by the catalytic oxidation reaction of 3,3,5,5-tetramethylbenzidine (TMB) in presence of H2O2, and a superior peroxidase-like activity of NiCo2O4 was confirmed by stronger absorbance at 652 nm. Furthermore, the proposed sensing platform showed commendable response to H2O2 with a linear range from 10 µM to 400 µM, and a detection limit of 0.21 µM. Cooperated with GOx, the developed novel colorimetric and visual glucose-sensing platform exhibited high selectivity, favorable reproducibility, satisfactory applicability, wide linear range (from 0.1 mM to 4.5 mM), and a low detection limit of 5.31 µM. In addition, the concentration-dependent color change would offer a better and handier way for detection of H2O2 and glucose by naked eye.