Geometric and Electronic Structural Engineering of Isolated Ni Single Atoms for a Highly Efficient CO2 Electroreduction.

Tuning the coordination environment and geometric structures of single atom catalysts is an effective approach for regulating the reaction mechanism and maximize the catalytic efficiency of single-atom centers. Here, a template-based synthesis strategy is proposed for the synthesis of high-density NiNx sites anchored on the surface of hierarchically porous nitrogen-doped carbon nanofibers (Ni-HPNCFs) with different coordination environments. First-principles calculations and advanced characterization techniques demonstrate that the single Ni atom is strongly coordinated with both pyrrolic and pyridinic N dopants, and that the predominant sites are stabilized by NiN3 sites. This dual engineering strategy increases the number of active sites and utilization efficiency of each single atom as well as boosts the intrinsic activity of each active site on a single-atom scale. Notably, the Ni-HPNCF catalyst achieves a high CO Faradaic efficiency (FECO ) of 97% at a potential of -0.7 V, a high CO partial current density (jCO ) of 49.6 mA cm-2 (-1.0 V), and a remarkable turnover frequency of 24 900 h-1 (-1.0 V) for CO2 reduction reactions (CO2 RR). Density functional theory calculations show that compared to pyridinic-type NiNx , the pyrrolic-type NiN3 moieties display a superior CO2 RR activity over hydrogen evolution reactions, resulting in their superior catalytic activity and selectivity.

Highly stable and durable ZnIn2S4 nanosheets wrapped oxygen deficient blue TiO2(B) catalyst for selective CO2 photoreduction into CO and CH4.

Developing new and highly stable efficient photocatalysts is crucial for achieving high performance and selective photocatalytic CO2 conversion. In this paper, we designed a one-dimensional oxygen-deficient blue TiO2(B) (BT) catalyst for improved electron mobility and visible light accessibility. In addition, hexagonal ZnIn2S4 (ZIS) nanosheets with a low bandgap and great visible light accessibility are employed to produce effective heterostructures with BT. The synthesized materials are tested for photocatalytic conversion of CO2 into solar fuels (H2, CO and CH4). The optimized composite yields 71.6 and 10.3 µmol g-1h-1 of CO and CH4, three and ten times greater than ZIS, respectively. When ZIS nanosheets are combined with a one-dimensional oxygen-deficient BT catalyst, improved electron mobility and visible light accessibility are achieved, charge carriers are effectively segregated, and the transfer process is accelerated, resulting in efficient CO2 reduction. The photocatalytic CO2 conversion activity of the constructed BT/ZIS heterostructures is very stable over a 10-day (240-hour) period, and CO and CH4 production rates increase linearly with time; however, as time goes on, the rates of H2 production decrease. Further, a five-time recycling test confirmed this, revealing essentially equal activity and selectivity throughout the experiment. As a result, CO2 to CO and CH4 conversion has high selectivity and longer durability. The band structure of the BT/ZIS composite is determined using Mott-Schottky measurement, diffuse reflectance spectroscopy, and valence band X-ray photoelectron spectroscopy. This research demonstrates a novel approach to investigating effective, stable, and selective photocatalytic CO2 reduction systems for solar-to-chemical energy conversion.

Plasmon-Sensitized Graphene/TiO2 Inverse Opal Nanostructures with Enhanced Charge Collection Efficiency for Water Splitting.

In this contribution we have developed TiO2 inverse opal based photoelectrodes for photoelectrochemical (PEC) water splitting devices, in which Au nanoparticles (NPs) and reduced graphene oxide (rGO) have been strategically incorporated (TiO2@rGO@Au). The periodic hybrid nanostructure showed a photocurrent density of 1.29 mA cm-2 at 1.23 V vs RHE, uncovering a 2-fold enhancement compared to a pristine TiO2 reference. The Au NPs were confirmed to extensively broaden the absorption spectrum of TiO2 into the visible range and to reduce the onset potential of these photoelectrodes. Most importantly, TiO2@rGO@Au hybrid exhibited a 14-fold enhanced PEC efficiency under visible light and a 2.5-fold enrichment in the applied bias photon-to-current efficiency at much lower bias potential compared with pristine TiO2. Incident photon-to-electron conversion efficiency measurements highlighted a synergetic effect between Au plasmon sensitization and rGO-mediated facile charge separation/transportation, which is believed to significantly enhance the PEC activity of these nanostructures under simulated and visible light irradiation. Under the selected operating conditions the incorporation of Au NPs and rGO into TiO2 resulted in a remarkable boost in the H2 evolution rate (17.8 µmol/cm2) compared to a pristine TiO2 photoelectrode reference (7.6 µmol/cm2). In line with these results and by showing excellent stability as a photoelectrode, these materials are herin underlined to be of promising interest in the PEC water splitting reaction.

Reduced graphene oxide wrapped core-shell metal nanowires as promising flexible transparent conductive electrodes with enhanced stability.

Transparent conductive electrodes (TCEs) are widely used in a wide range of optical-electronic devices. Recently, metal nanowires (NWs), e.g. Ag and Cu, have drawn attention as promising flexible materials for TCEs. Although the study of core-shell metal NWs, and the encapsulation/overcoating of the surface of single-metal NWs have separately been an object of focus in the literature, herein for the first time we simultaneously applied both strategies in the fabrication of highly stable Ag-Cu NW-based TCEs by the utilization of Ag nanoparticles covered with reduced graphene oxide (rGO). The incorporation of Ag nanoparticles by galvanic displacement reaction was shown to significantly increase the long term stability of the electrode. Upon comparison with a CuNW reference, our novel rGO/Cu-AgNW-based TCEs unveiled remarkable opto-electrical properties, with a 3-fold sheet resistance decrease (from 29.8 Ω sq-1 to 10.0 Ω sq-1) and an impressive FOM value (139.4). No detrimental effect was noticed in the relatively high transmittance value (T = 77.6% at 550 nm) characteristic of CuNWs. In addition, our rGO/Cu-AgNW-based TCEs exhibited outstanding thermal stability up to 20 days at 80 °C in air, as well as improved mechanical flexibility. The superior performance herein reported compared with both CuNWs and AgNWs, and with a current conventional ITO reference, is believed to highlight the great potential of these novel materials as promising alternatives in optical-electronic devices.

Viable method for the synthesis of biphasic TiO2 nanocrystals with tunable phase composition and enabled visible-light photocatalytic performance.

Here we demonstrate a facile method to synthesize high-surface-area TiO(2) nanoparticles in aqueous-ethanol system with tunable brookite/rutile and brookite/anatase ratio possessing high surface area that exhibits enhanced photoactivity. Titanium tetrachloride (TiCl(4)) is used as the metal precursor of choice and the tuning of phase compositions are achieved by varying the water:ethanol ratio, used as mixed solvent system. The synthesized samples were characterized in detail using X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), BET nitrogen sorption measurements, and UV-vis diffuse reflectance spectroscopy (UV-DRS). The photocatalytic activity of biphasic TiO(2) nanocrystals was evaluated by following the degradation kinetics of rhodamine-B dye in aqueous solution and under visible light. Mixed-phase TiO(2) nanostructures composing 83% brookite and 17% of rutile exhibited superior photoactivity when compared to Degussa P25 and phase-pure anatase nanocrystals. The exceptional photocatalytic activity of the synthesized nanostructures can be elucidated on the account of their large surface area and biphasic composition. On the basis of the detailed investigation reported herein, we conclude that tuning the ethanol volume in the mixed-solvent reaction system holds the key to tailor and control the final TiO(2) phase obtained.

A facile and green approach for the controlled synthesis of porous SnO2 nanospheres: application as an efficient photocatalyst and an excellent gas sensing material.

A facile and elegant methodology invoking the principles of Green Chemistry for the synthesis of porous tin dioxide nanospheres has been described. The low-temperature (∼50 °C) synthesis of SnO2 nanoparticles and their self-assembly into organized, uniform, and monodispersed porous nanospheres with high surface area is facilitated by controlling the concentration of glucose, which acts as a stabilizing as well as structure-directing agent. A systematic control on the stannate to glucose molar concentration ratio determines the exact conditions to obtain monodispersed nanospheres, preferentially over random aggregation. Detailed characterization of the structure, morphology, and chemical composition reveals that the synthesized material, 50 nm SnO2 porous nanospheres possess BET surface area of about 160 m²/g. Each porous nanosphere consists of a few hundred nanoparticles ∼2-3 nm in diameter with tetragonal cassiterite crystal structure. The SnO2 nanospheres exhibit elevated photocatalytic activity toward methyl orange with good recyclability. Because of the high activity and stability of this photocatalyst, the material is ideal for applications in environmental remediation. Moreover, SnO2 nanospheres display excellent gas sensing capabilities toward hydrogen. Surface modification of the nanospheres with Pd transforms this sensing material into a highly sensitive and selective room-temperature hydrogen sensor.