Constructing cuprous oxide-modified zinc tetraphenylporphyrin ultrathin nanosheets heterojunction for enhanced photocatalytic carbon dioxide reduction to methane.

The application of supermolecular naonostructures in the photocatalytic carbon dioxide reduction reaction (CO2RR) has attracted increasing attentions. However, it still faces significant challenges, such as low selectivity for multi-electron products and poor stability. Here, the cuprous oxide (Cu2O)-modified zinc tetraphenylporphyrin ultrathin nanosheets (ZnTPP NSs) are successfully constructed through the aqueous chemical reaction. Comprehensive characterizations confirm the formation of type-II heterojunction between Cu2O and ZnTPP in Cu2O@ZnTPP, and the electron transfer from Cu2O to ZnTPP through the Zn-O-Cu bond under the static contact. Under the visible-light irradiation (λ > 420 nm), the optimized Cu2O@ZnTPP sample as catalyst for photocatalytic CO2RR exhibits the methane (CH4) evolution rate of 120.9 µmol/g/h, which is âˆ¼ 4 and âˆ¼ 10 times those of individual ZnTPP NSs (28.0 µmol/g/h) and Cu2O (12.8 µmol/g/h), respectively. Meanwhile, the CH4 selectivity of âˆ¼ 98.7 % and excellent stability can be achieved. Further experiments reveal that Cu2O@ZnTPP has higher photocatalytic conversion efficiency than Cu2O and ZnTPP NSs, and the photoinduced electron transfer from ZnTPP to Cu2O can be identified via the path of ZnTPP→ (ZnTPP•ZnTPP)*→ ZnTPP-→ Zn-O-Cu â†’ Cu2O. Consequently, Cu2O@ZnTPP exhibits a shorter electron-hole separation lifetime (3.3 vs. 9.3 ps) and a longer recombination lifetime (23.1 vs. 13.4 ps) than individual ZnTPP NSs. This work provides a strategy to construct the organic nanostructures for photocatalytic CO2RR to multi-electron products.

Construction of Cobalt Porphyrin-Modified Cu2 O Nanowire Array as a Tandem Electrocatalyst for Enhanced CO2 Reduction to C2 Products.

Here, the molecule-modified Cu-based array is first constructed as the self-supporting tandem catalyst for electrocatalytic CO2 reduction reaction (CO2 RR) to C2 products. The modification of cuprous oxide nanowire array on copper mesh (Cu2 O@CM) with cobalt(II) tetraphenylporphyrin (CoTPP) molecules is achieved via a simple liquid phase method. The systematical characterizations confirm that the formation of axial coordinated Co-O-Cu bond between Cu2 O and CoTPP can significantly promote the dispersion of CoTPP molecules on Cu2 O and the electrical properties of CoTPP-Cu2 O@CM heterojunction array. Consequently, as compared to Cu2 O@CM array, the optimized CoTPP-Cu2 O@CM sample as electrocatalyst can realize the 2.08-fold C2 Faraday efficiency (73.2% vs 35.2%) and the 2.54-fold current density (-52.9 vs -20.8 mA cm-2 ) at -1.1 V versus RHE in an H-cell. The comprehensive performance is superior to most of the reported Cu-based materials in the H-cell. Further study reveals that the CoTPP adsorption on Cu2 O can restrain the hydrogen evolution reaction, improve the coverage of * CO intermediate, and maintain the existence of Cu(I) at low potential.

Ultrathin covalent organic framework nanosheets for enhanced photocatalytic water oxidation.

Photocatalytic water oxidation is a key half-reaction for various solar-to-fuel conversion systems but requires simultaneous water affinity and hole accumulation at the photocatalytic site. Here, we present the rational design and synthesis of an ionic-type covalent organic framework (COF) named tetraphenylporphyrin cobalt and cobalt bipyridine complex (CoTPP-CoBpy3) COF, combining cobalt porphyrin and cobalt bipyridine building blocks as a photocatalyst for water oxidation. The good dispersibility of porous large-size (>2 micrometers) COF nanosheets (≈1.45 nanometers) facilitates local water collection; the ultrafast triplet-state charge transfer (1.8 picoseconds) and prolonged charge separation (1.2 nanoseconds) further contribute to the efficient accumulation of holes in the CoTPP moiety, leading to a photocatalytic dioxygen production rate of 7323 micromoles per gram per hour. Moreover, we have identified an end-on superoxide radical (O2·) intermediate at the active site of the CoTPP moiety and proposed an electron-intermediate cascade mechanism that elucidates the synergistic coupling of electron relay (S1-T1-T1') and intermediate evolution during the photocatalytic process.

Construction of graphene oxide-coated zinc tetraphenyporphyrin nanostructures for photocatalytic CO2 reduction to highly selective CH4 product.

The zinc-based photocatalysts for CO2 reduction have attracted increasing attention, however, usually exhibit low CO2-to-CH4 selectivity. Here, the graphene oxide (GO)-coated zinc tetraphenylporphyrin (ZnTPP/GO) nanocomposites are successfully synthesized through a simple method. It is found that with the increase of GO content, the crystallinity of ZnTPP nanocrystals enhances with the size decrease, and then the light absorption can easily match with the solar spectrum. The optimal ZnTPP/GO sample exhibits the CH4 evolution rate of 41.6 µmol g-1 h-1 and CH4 selectivity of >95%, which are higher than those of ZnTPP nanocrystals (7.8 µmol g-1 h-1 and 50.3%). The systematic characterizations confirm that the generation of axial coordinated ZnOC bonds between ZnTPP and GO plays a key role in the formation of ZnTPP/GO nanostructure and their synergic effect on photocatalytic CO2 reduction. The encapsulation of GO on ZnTPP nanocrystals not only promotes the CO2 adsorption, interfacial reaction, and stability, but also accelerates the separation of photoinduced carriers on ZnTPP (0.1 ps vs. 425.9 ps), the transportation from ZnTPP to GO (2.3 ps vs. 83.6 ps), and their final enrichment on GO. This work provides a new strategy to apply graphene and organic nanomaterials in artificial photosynthesis.

Heterostructure of Semiconductors on Self-Supported Cuprous Phosphide Nanowires for Enhanced Overall Water Splitting.

Rational design, controllable synthesis, and an in-depth mechanism study of Cu-based bifunctional semiconductor heterostructures toward overall water splitting (OWS) are imperative but still face challenges. Herein, n-type iron oxide and p-type nickel phosphide and cobalt phosphide are respectively coupled with p-type cuprous phosphide nanowires on Cu foams via a general growth-phosphorization strategy. These self-supported semiconductor heterojunctions with different built-in potentials (EBI) are used as binder-free electrodes for OWS and exhibit significantly improved electrocatalytic activities compared to their counterparts. Among them, the heterostructure with the largest EBI of 1.57 V attains the smallest overpotential of 97 mV at 10 mA cm-2 for the hydrogen evolution reaction and 243 mV at 50 mA cm-2 for the oxygen evolution reaction in 1 M KOH. The corresponding two-electrode electrolyzer requires a cell voltage of 1.685 V at 50 mA cm-2 and shows admirable long-term stability at 100 mA cm-2 with a Faraday efficiency of around 98%. These promoted electrocatalytic performances originate from the enhanced active site, accelerated charge transfer, enlarged electrochemical active surface area, and synergy between different components at the heterointerface. This work represents a promising avenue to construct cost-efficient semiconductor heterostructures as bifunctional electrocatalysts applied to the sustainable energy industry.

Assembly of Cobalt Layered Double Hydroxide on Cuprous Phosphide Nanowire with Strong Built-In Potential for Accelerated Overall Water Splitting.

Heterostructure plays an important role in boosting the overall water splitting (OWS) performance of nonprecious metal electrocatalysts. However, rational design and synthesis of semiconductor heterojunctions especially for Cu-based ones as efficient bifunctional electrocatalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) still face challenges, and the in-depth study of catalytic mechanisms is urgently needed. Herein, n-type cobalt layered double hydroxide nanosheets are assembled on p-type cuprous phosphide nanowire to form p-n junction. This heterostructure with a strong built-in potential (EBI ) of 1.78 V provides enlarged electrochemical active surface area, enhanced active site, facilitated electron separation and transfer, and accelerated formation of superoxide radical. As expected, the heterogeneous electrocatalyst exhibits significantly improved activities for OWS, achieving an overpotential of 111 mV for HER and 221 mV for OER and an applied voltage of 1.575 V for OWS at 10 mA cm-2 in 1 m KOH. Moreover, the overpotentials are further decreased under visible light irradiation. This work represents a new insight into Cu-based catalysts toward OWS and an approach based on EBI to design semiconductor heterostructure promising for renewable energy applications.

A fluorometric displacement assay for adenosine triphosphate using layered cobalt(II) double hydroxide nanosheets.

A turn-on fluorometric method is described for the determination of adenosine-5'-triphosphate (ATP). It is based on the displacement of a dye-labeled oligonucleotide from a cobalt(II) based layered double hydroxide (LDH). Due to the electrostatic and ligand exchange interaction, the FAM-labeled DNA is readily adsorbed on the LDH. This leads to complete and fast quenching of the green fluorescence of the label. However, on addition of ATP, the DNA is detached from the LDH because of the stronger affinity of ATP for LDH. This results in the restoration of the green fluorescence. The effect was used to design a sensitive assay that has a linear response in the 0.5-100 µM ATP concentration range and a 0.23 µM lower detection limit. It was applied to the determination of ATP in spiked serum samples. Graphical abstract Schematic presentation of a fluorometric ATP assay based on the displacement of a dye-labeled oligonucleotide from a layered double hydroxide (LDH).

Chemical redox modulated fluorescence of nitrogen-doped graphene quantum dots for probing the activity of alkaline phosphatase.

Alkaline phosphatase (ALP) as an essential enzyme plays an important role in clinical diagnoses and biomedical researches. Hence, the development of convenient and sensitivity assay for monitoring ALP is extremely important. In this work, on the basis of chemical redox strategy to modulate the fluorescence of nitrogen-doped graphene quantum dots (NGQDs), a novel label-free fluorescent sensing system for the detection of alkaline phosphatase (ALP) activity has been developed. The fluorescence of NGQDs is firstly quenched by ultrathin cobalt oxyhydroxide (CoOOH) nanosheets, and then restored by ascorbic acid (AA), which can reduce CoOOH to Co2+, thus the ALP can be monitored based on the enzymatic hydrolysis of L-ascorbic acid-2-phosphate (AAP) by ALP to generate AA. Quantitative evaluation of ALP activity in a range from 0.1 to 5U/L with the detection limit of 0.07U/L can be realized in this sensing system. Endowed with high sensitivity and selectivity, the proposed assay is capable of detecting ALP in biological system with satisfactory results. Meanwhile, this sensing system can be easily extended to the detection of various AA-involved analytes.

Multisource Synergistic Electrocatalytic Oxidation Effect of Strongly Coupled PdM (M = Sn, Pb)/N-doped Graphene Nanocomposite on Small Organic Molecules.

A series of palladium-based catalysts of metal alloying (Sn, Pb) and/or (N-doped) graphene support with regular enhanced electrocatalytic activity were investigated. The peak current density (118.05 mA cm(-2)) of PdSn/NG is higher than the sum current density (45.63 + 47.59 mA cm(-2)) of Pd/NG and PdSn/G. It reveals a synergistic electrocatalytic oxidation effect in PdSn/N-doped graphene Nanocomposite. Extend experiments show this multisource synergetic catalytic effect of metal alloying and N-doped graphene support in one catalyst on small organic molecule (methanol, ethanol and Ethylene glycol) oxidation is universal in PdM(M = Sn, Pb)/NG catalysts. Further, The high dispersion of small nanoparticles, the altered electron structure and Pd(0)/Pd(II) ratio of Pd in catalysts induced by strong coupled the metal alloying and N-doped graphene are responsible for the multisource synergistic catalytic effect in PdM(M = Sn, Pb) /NG catalysts. Finally, the catalytic durability and stability are also greatly improved.

Controlled morphogenesis of organic polyhedral nanocrystals from cubes, cubooctahedrons, to octahedrons by manipulating the growth kinetics.

Morphological control of organic nanocrystals (ONCs) is important in the fields ranging from specialty chemicals to molecular semiconductors. Although the thermodynamic shape can be readily predicted, most growth morphologies of ONCs are actually determined by kinetic factors and remain poorly understood. On the basis of the reduction of zinc tetraphenylporphyrin perchlorate (ZnTPP(+)ClO(4)(-)) with sodium nitrite (Na(+)NO(2)(-)), we synthesized two series of ONCs of aquozinc tetraphenylporphyrin (ZnTPP·H(2)O), in the presence of either cetyltrimethylammonium bromide (CTAB) or poly(vinyl pyrrolidone) (PVP) as the capping ligands. As the cationic precursors of ZnTPP(+) are separated in the solution phase, smoothly controlled release of ZnTPP·H(2)O building blocks via the reduction reaction facilitates the separation between the nucleation and growth stages during the formation of ONCs and provides a high and tunable supersaturation unavailable by employing conventional crystallization techniques. We found that CTAB mainly serve as the colloidal stabilizer, while selective adhesion of PVP on the {020}s facet alters the crystal habits significantly. In both cases, manipulation of the growth kinetics had been achieved by adjusting the concentration of ZnTPP·H(2)O growth units, and consequently, the supersaturation for the crystallization, thus yielding ONCs with well-controlled sizes and shapes. Remarkably, thermodynamically stable octahedrons have been obtained at high supersaturation in both CTAB and PVP cases.

Superhydrophobic pure silver surface with flower-like structures by a facile galvanic exchange reaction with [Ag(NH3)2]OH.

Superhydrophobic pure silver film composed of flower-like microstructures built by interconnected silver nanoplates on a copper plate without any modification was prepared by a facile galvanic exchange reaction between the aqueous [Ag(NH3)2]OH and the copper plate, giving rise to a contact angle as high as 157 degrees .

Organic core/diffuse-shell nanorods: fabrication, characterization and energy transfer.

We successfully prepared organic core/diffuse-shell nanorods, which presents fluorescence resonance energy transfer from the core to shell components.

Colloid chemical reaction route to the preparation of nearly monodispersed perylene nanoparticles: size-tunable synthesis and three-dimensional self-organization.

By employing a colloid chemical reaction method we demonstrate the preparation of organic nanoparticles composed of perylene molecules (PeNPs) based on the reduction of perylene perchlorate by Br- anions in the presence of cetyl trimethyl ammonium bromide (CTA+Br-) in acetonitrile. A discrete nucleation event, followed by a slower controlled growth on the existing particles, is identified during formation of PeNPs. By changing the growth parameters, such as the monomer concentration and the method of injection, quasi-spherical PeNPs with controllable sizes from 25 to 90 nm could be obtained. The homogeneous solution phase of this method makes it capable of large-scale synthesis of PeNPs with a size distribution (<10%) that is improved by formation of a protective layer of CTA+ around the PeNPs. The three-dimensional, hierarchical self-organization of 25-nm PeNPs building blocks is observed to form nanobelts and square nanorods, possibly templated by the CTA+ lamellar micelle structures in acetonitrile. Spectroscopic results reveal two kinds of trends in the development of the optical properties of perylene as they evolve from the molecular to the bulk phase in the nanometer range. The so-called size dependence is evidenced by a switch from Y-type to E-type excimers as the size of the PeNPs increased from 25 to 90 nm. As the 25-nm PeNPs organize into nanobelts or square nanorods the oscillator strength of the Y-type excimers is relatively enhanced. That is, collective phenomena develop as the proximal particles interact in the glassy solids. Our very recent results indicate that this colloid chemical reaction method can also be applied to other organic compounds.