Graphitic Carbon Nitride Nanosheets Decorated with Zinc-Cadmium Sulfide for Type-II Heterojunctions for Photocatalytic Hydrogen Production.

In this study, we fabricated graphitic carbon nitride (g-C3N4) nanosheets with embedded ZnCdS nanoparticles to form a type II heterojunction using a facile synthesis approach, and we used them for photocatalytic H2 production. The morphologies, chemical structure, and optical properties of the obtained g-C3N4-ZnCdS samples were characterized by a battery of techniques, such as TEM, XRD, XPS, and UV-Vis DRS. The as-synthesized g-C3N4-ZnCdS photocatalyst exhibited the highest hydrogen production rate of 108.9 µmol·g-1·h-1 compared to the individual components (g-C3N4: 13.5 µmol·g-1·h-1, ZnCdS: 45.3 µmol·g-1·h-1). The improvement of its photocatalytic activity can mainly be attributed to the heterojunction formation and resulting synergistic effect, which provided more channels for charge carrier migration and reduced the recombination of photogenerated electrons and holes. Meanwhile, the g-C3N4-ZnCdS heterojunction catalyst also showed a higher stability over a number of repeated cycles. Our work provides insight into using g-C3N4 and metal sulfide in combination so as to develop low-cost, efficient, visible-light-active hydrogen production photocatalysts.

Engineering at Subatomic Scale: Achieving Selective Catalytic Pathways via Tuning of the Oxidation States in Functionalized Single-Atom Quantum Catalysts.

Regulating the catalytic pathways of single-atom sites in single atom catalysts (SACs) is an exciting debate at the moment, which has redirected the research towards understanding and modifying the single-atom catalytic sites through various strategies including altering the coordination environment of single atom for desirable outcomes as well as increasing their number. One useful aspect concerning the tunability of the catalytic pathways of SACs, which has been overlooked, is the oxidation state dynamics of the single atoms. In this study, iron single-atoms (FeSA) with variable oxidation states, dependent on the precursors, are harnessed inside a nitrogen-rich functionalized carbon quantum dots (CQDs) matrix via a facile one-step and low-temperature synthesis process. Dynamic electronic properties are imparted to the FeSAs by the simpler carbon dots matrix of CQDs in order to achieve the desired catalytic pathways of reactive oxygen species (ROS) generation in different environments, which are explored experimentally and theoretically for an in-depth understanding of the redox chemistry that drives the alternative catalytic pathways in FeSA@CQDs. These alternative and oxidation state-dependent catalytic pathways are employed for specific as well as cascade-like activities simulating natural enzymes as well as biomarkers for the detection of cancerous cells.

Identification of Molecular Fluorophore as a Component of Carbon Dots able to Induce Gelation in a Fluorescent Multivalent-Metal-Ion-Free Alginate Hydrogel.

We introduce a simple approach to fabricate fluorescent multivalent metal ion-free alginate hydrogels, which can be produced using carbon dots accessible from natural sources (citric acid and L-cysteine). Molecular fluorophore 5-oxo-2,3-dihydro-5H-[1,3]-thiazolo[3,2-a] pyridine-3,7-dicarboxylic acid (TPDCA), which is formed during the synthesis of carbon dots, is identified as a key segment for the crosslinking of hydrogels. The crosslinking happens through dynamic complexation of carboxylic acid groups of TPDCA and alginate cages along with sodium ions. The TPDCA derived hydrogels are investigated regarding to their thermal, rheological and optical properties, and found to exhibit characteristic fluorescence of this aggregated molecular fluorophore. Moreover, gradient hydrogels with tunable mechanical and optical properties and controlled release are obtained upon immersion of the hydrogel reactors in solutions of divalent metal ions (Ca2+, Cu2+, and Ni2+) with a higher affinity to alginate.

Interfacial Phenomenon and Nanostructural Enhancements in Palladium Loaded Lanthanum Hydroxide Nanorods for Heterogeneous Catalytic Applications.

Hydrogenation and cross-coupling reactions are of great importance for industrial applications and noble metal based catalysts are filling the void since the last few decades. However, the high cost of noble metals and poor recycling performance provides an opportunity for chemists to look for alternate options. Herein, we present the use of Lanthanum hydroxide as support for loading ultra-low amount of Pd for hydrogenation and cross-coupling reactions. Lanthanum hydroxide having controlled morphologies comprises exposed crystallographic facets which interact with small sized Pd NPs and shows versatile and effective catalytic performance. The reduction of 4-NP over Pd/La(OH)3 was achieved within very short time (45s) with a rate constant of 60 × 10-3 s-1. The hydrogenation of styrene was also accomplished within 1 hour with much high TOF value (3260 h-1). Moreover, the Suzuki cross-couplings of iodobenzene and phenyl boronic acid into biphenyl completed within 35 min with a TOF value of 389 h-1. The strong interfacial electronic communication regulates electron density of catalytic sites and lowers energy for adsorption of reactant and subsequently conversion into products. Moreover, abundant hydroxyl groups on the surface of La(OH)3, large surface area, mono-dispersity and ultra-small size of Pd NPs also favors the efficient conversion of reactants.

Synergistic effect of Co-Ni co-bridging with MoS2 nanosheets for enhanced electrocatalytic hydrogen evolution reactions.

The depletion of fossil fuels and associated environmental problems have drawn our attention to renewable energy resources in order to meet the global energy demand. Electrocatalytic hydrogen evolution has been considered a potential energy solution due of its high energy density and environment friendly technology. Herein, we have successfully synthesized a noble-metal-free Co-Ni/MoS2 nanocomposite for enhanced electrocatalytic hydrogen evolution. The nanocomposite has been well characterized using HRTEM, elemental mapping, XRD, and XPS analysis. The as-synthesized nanocomposite exhibits a much smaller onset potential and better current density than those of Co-MoS2, Ni-MoS2 and MoS2, with a Tafel value of 49 mV dec-1, which is comparable to that of a commercial Pt/C catalyst. The synergistic effect and interfacial interaction of Co-Ni bimetallic nanoparticles enhances the intrinsic modulation in the electronic structure resulting in an improved HER performance. Moreover, the electrochemical impedance spectroscopic results suggest smaller resistance values for the Co-Ni/MoS2 nanocomposite, compared to those for the charge transfer of bare nanosheets, which increase the faradaic process and in turn enhance the HER kinetics for a better performance. Our as-synthesized Co-Ni/MoS2 nanocomposite holds great potential for the future synthesis of noble-metal-free catalysts.

Highly Efficient Photocatalytic Z-Scheme Hydrogen Production over Oxygen-Deficient WO3-x Nanorods supported Zn0.3Cd0.7S Heterostructure.

The demand for clean renewable energy is increasing due to depleting fossil fuels and environmental concerns. Photocatalytic hydrogen production through water splitting is one such promising route to meet global energy demands with carbon free technology. Alternative photocatalysts avoiding noble metals are highly demanded. Herein, we fabricated heterostructure consist of oxygen-deficient WO3-x nanorods with Zn0.3Cd0.7S nanoparticles for an efficient Z-Scheme photocatalytic system. Our as obtained heterostructure showed photocatalytic H2 evolution rate of 352.1 µmol h-1 with apparent quantum efficiency (AQY) of 7.3% at λ = 420 nm. The photocatalytic hydrogen production reaches up to 1746.8 µmol after 5 hours process in repeatable manner. The UV-Visible diffuse reflectance spectra show strong absorption in the visible region which greatly favors the photocatalytic performance. Moreover, the efficient charge separation suggested by electrochemical impedance spectroscopy and photocurrent response curves exhibit enhancement in H2 evolution rate. The strong interface contact between WO3-x nanorods and Zn0.3Cd0.7S nanoparticles ascertained from HRTEM images also play an important role for the emigration of electron. Our findings provide possibilities for the design and development of new Z-scheme photocatalysts for highly efficient hydrogen production.