Ni1−xCoxSe2?C/ZnIn2S4 Hybrid Nanocages with Strong 2D/2D Hetero-Interface Interaction Enable Efficient H2-Releasing Photocatalysis

Designing a semiconductor-based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron-hole pairs is highly important for enhancing H₂ releasing photocatalysis. Here, a new class of Ni_1−xCo_xSe₂–C/ZnIn₂S₄ hierarchical nanocages with abundant and compact ZnIn₂S₄ nanosheets/Ni_1−xCo_xSe₂^ C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero-junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C, improving the separation and transfer of photo-generated electron-hole pairs. As a consequence, the distinctive Ni_1−xCo_xSe₂ C/ZnIn₂S₄ hierarchical nanocages without using additional noble-metal cocatalysts, display remarkable H₂-relaesing photocatalytic activity with a rate of 5.10 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn₂S₄ nanosheets and bare Ni_1−xCo_xSe₂ C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C 2D/2D hetero-interfaces can powerfully promote the separation of photo-generated charge carriers and the electrons transfer from ZnIn₂S₄ to Ni_1−xCo_xSe₂ C.     

Engineering 2D Arsenic-Phosphorus Theranostic Nanosheets

As an anticancer drugs, arsenic trioxide (ATO) has been certified to efficiently treat refractory acute promyelocytic leukemia (APL). Unfortunately it suffers from limited therapeutic potency for solid tumors due to its in vivo restricted administration dose and rapid renal clearance. Herein, distinct 2D arsenic-phosphorus (AsP) nanosheets are engineered by adopting an alloy strategy followed by exfoliation, which can confine toxic arsenic into AsP crystals, thus significantly improving the biosafety and biocompatibility of arsenic-based chemotherapeutic drugs. Of particular note, the high light absorption and strong photothermal-conversion efficiency (37.6%) in the second near infrared biowindow (NIR-II) of AsP nanosheets not only endow them with desirable contrast-enhanced photoacoustic imaging properties, but also achieve efficient local tumor hyperthermia, which further synergistically triggers the in-situ transformation from low toxic/nontoxic AsP crystals into highly toxic arsenic species, exerting a strong arsenic-mediated antineoplastic effect. Both in vitro and in vivo data verify the synergy between photonic therapy in NIR-II and enhanced chemotherapy as enabled by AsP nanosheets, paving the way for efficient nanomedicine-enabled arsenic-based chemotherapeutic tumor treatment.     

Highly stable γ-NiOOH/ZnCdS photocatalyst for efficient hydrogen evolution

It is extremely desirable to develop high hydrogen evolution activity and stable visible-light-driven photocatalysts. The sluggish oxidation process and holes accumulation are the main obstacles to high catalysis activity and photo-stability. An efficient γ-NiOOH/ZnCdS photocatalyst was prepared by in-situ hydrothermal method. The γ-NiOOH nanosheets distribute on ZnCdS nanospheres surface and accelerate holes transfer. The hydrogen evolution rate is up to 48.60 mmol g^?1 h^?1 under visible-light illumination (λ = 400–780 nm), about 10.8 times of pure ZnCdS (4.50 mmol g^?1 h^?1) and 1.8 times of general β-NiOOH modified ZnCdS (27.40 mmol g^?1 h^?1). And apparent quantum yield of γ-NiOOH/ZCS-100 is up to 18.23% (400 nm). The carrier lifetime extends from 5.50 ns (ZnCdS) to 6.10 ns (γ-NiOOH/ZCS), examined by steady photoluminescence and time-resolved photoluminescence. Moreover, the γ-NiOOH/ZCS photocatalyst has exhibited excellent photo-stability even after one-year of storage. The γ-NiOOH nanosheets can be an excellent co-catalyst on accelerating both holes transfer and oxidation process for high photo-stability and photo-activity.     

Amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets as Janus electrocatalyst for efficient water splitting

Efficient and sustainable Janus catalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly desirable for future hydrogen production via water electrolysis. Herein we report an active Janus electrocatalyst of amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets on nickel foam (CoMoP/CoP/NF) for efficient electrolysis of alkaline water. As-reported CoMoP/CoP/NF consists of amorphous bimetal phosphide nanosheets doped with crystalline CoMoP/CoP heterostructured nanoparticles on NF. It can efficiently catalyze both HER (η = 127 mV@100 mA cm^?2) and OER (η = 308 mV@100 mA cm^?2) in alkaline electrolyte with long-term durability. Serving as anode and cathode of water electrolyzer, CoMoP/CoP/NF generates electrolytic current of 10, 50 and 100 mA cm^?2 at low voltage of 1.50, 1.59, and 1.67 V, respectively.     

Step-scheme perylenediimide supramolecular nanosheet and TiO2 nanoparticle composites for boosted water splitting performance

Adjusting the band gap of organic-inorganic composites by chemical bonding can effectively construct Step-scheme (S-scheme) heterojunctions, featuring properties of fast photogenerated charge migration and excellent photocatalytic performance. In this work, a novel perylene-3, 4, 9, 10-tetracarboxylicdiimide (PDI)-titanium dioxide (TiO₂) heterojunction is elaborately synthesized through simple solvent compounding method. The monodispersed spherical TiO₂ nanoparticles was prepared with the capping agents of oleylamine and oleic acid, and suffered by a ligand exchange process with nitrosonium tetrafluoroborate (NOBF₄) to remove oleylamine and oleic acid. The NOBF₄ ligands were further replaced by PDI super molecular nanosheets to obtain two dimensional (2D)-zero dimensional (0D) PDI-TiO₂ composites. TiO₂ nanoparticles are evenly anchored on the surface of PDI nanosheets with intimate contact. The PDI-TiO₂ composites has emerged considerably superior activity in hydrogen evolution. The highest hydrogen evolution rate for PDI-TiO₂composites with the PDI weight percentage of 2.4% was 9766 μmol h^?1 g^?1 under solar light irradiation, which is 2.56 times of TiO₂-NOBF₄ catalyst. Moreover, PDI-TiO₂ composites possess stoichiometric overall water splitting performance with H₂ and O₂ release rates of 238.20 and 114.18 μmol h^?1 g^?1. The superior photocatalytic performance of PDI-TiO₂ composites can be attributed to the dramatic increase in visible and NIR light absorption caused by π-π stacking structure of PDI, the prevented charge recombination by the S-scheme heterojunction, and the enhanced oxygen evolution by the stronger oxidation capability of PDI. PDI supramolecular nanosheets may work as a novel functional support for many types of semiconductor nanomaterials as graphene, which will display a wide range of application prospects in the energy and environmental fields.     

Graphitic-C3N4/ZnCr-layered double hydroxide 2D/2D nanosheet heterojunction: Mesoporous photocatalyst for advanced oxidation of azo dyes with in situ produced H2O2

In this study the constructional modification of Graphitic carbon nitride nanosheet (GCN-ns) has been made with the aid of ZnCr layered double hydroxide (ZC-LDH) in a unique 2D-2D structure to enhance its visible light absorption. Optical and morphological study presents successful incorporation of ZC-LDH on the surface of GCN-ns. Through adjusting of GCN-ns by ZC-LDH lower recombination rate of e^?/h⁺ pairs, longer lifetimes and an increase in contamination reduction was brought out. The binary nanocomposite was employed to effectively degrade Rhodamine B under UV/vis light irradiation. The improvement in photocatalytic abilities was proven to be related to in situ self-production of H₂O₂ on GCN-ns/ZC-LDH surface by Xe light irradiation which in return accounts for additional hydroxide radical generation. Radical quenching experiments specified the main active species involved while the consequent step-scheme (S-scheme) charge transfer mechanism was proposed.     

Hierarchical porous transition metal oxide nanosheets templated from waste bagasse: General synthesis and Li/Na storage performance

As a promising anode candidate, hierarchical porous transition metal oxide nanosheets (TMO-NSs) have attracted significant interest due to their various advantages of abundant active sites, high specific capacity and shortened ion/electrons transport pathways. Although the TMO-NSs have been developed in the past decades, the previous synthesis strategies have some drawbacks such as high cost, complex synthesis techniques, and the requirement of special instruments. Herein, we develop a generalized and facile biomorphic method to synthesize various controllable hierarchical porous TMO-NSs by using waste bagasse as biotemplate. Furthermore, the porosity and pore size of as-prepared hierarchical porous TMO-NSs can be adjusted by changing the precursor solution concentration. Novel hierarchical porous TMO-NSs have been successfully prepared for many ternary or binary TMO, such as NiFe₂O₄, ZnFe₂O₄, ZnMn₂O₄, NiO and ZnO. Owing to their unique nanostructure, as-synthesized hierarchical porous TMO-NSs show an excellent electrochemical performance when used as anode for Li/Na-ion batteries. We believe that various hierarchical porous TMO-NSs available from the green, economical and convenient biomorphic strategy may lead to further developments in research and application on TMO-NSs materials.     

CNT-interconnected iron-doped NiP2/Ni2P heterostructural nanoflowers as high-efficiency electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) plays a decisive role in electrolytic water splitting. However, it is still challengeable to develop low-cost and efficient OER electrocatalysts. Herein, we present a combination strategy via heteroatom doping, hetero-interface engineering and introducing conductive skeleton to synthesize a hybrid OER catalyst of CNT-interconnected iron-doped NiP₂/Ni₂P (Fe-(NiP₂/Ni₂P)@CNT) heterostructural nanoflowers by a simple hydrothermal reaction and subsequent phosphorization process. The optimized Fe-(NiP₂/Ni₂P)@CNT catalyst delivers an ultralow Tafel slope of 46.1 mV dec^?1 and overpotential of 254 mV to obtain 10 mA cm^?2, which are even better than those of commercial OER catalyst RuO₂. The excellent OER performance is mainly attributed to its unique nanoarchitecture and the synergistic effects: the nanoflowers constructed by a 2D-like nanosheets guarantee large specific area and abundant active sites; the highly conductive CNT skeleton and the electronic modulation by the heterostructural NiP₂/Ni₂P interface and the hetero-atom doping can improve the catalytic activity; porous nanostructure benefits electrolyte penetration and gas release; most importantly, the rough surface and rich defects caused by phosphorization process can further enhance the OER performance. This work provides a deep insight to boost catalytic performance by heteroatom doping and interface engineering for water splitting.     

Highly dispersed cobalt nanoparticles onto nitrogen-doped carbon nanosheets for efficient hydrogen generation via catalytic hydrolysis of sodium borohydride

Porous carbon nanostructures are promising supports for stabilizing the highly dispersed metal nanoparticles and facilitating the mass transfer during the reaction, which are critical to achieve the high efficiency of hydrogen generation from sodium borohydride dehydrogenation. Herein, the catalytically active porous architectures are simply prepared by using 2-methylimidazole and melamine as reactive sources. The structural and compositional characterizations reveal the coexistence of metallic cobalt and N-doped carbon in porous architectures. Electron microscopy observations indicate that the synthesized products are smartly constructed from the carbon nanosheets with densely dispersed Co nanoparticles. Due to the notable structural features, the prepared Co@NC-600 sample presents the highly efficient activity for catalytic hydrolysis of NaBH₄ with a hydrogen generation rate of 2574 mL min⁻¹ g_cat⁻¹ and an activation energy of 47.6 kJ mol⁻¹. The catalytically active metallic Co and suitable support-effect of N-doped carbon are responsible for catalytic dehydrogenation.