Orange-peel derived carbon-loaded low content ruthenium nanoparticles as ultra-high performance alkaline water HER electrocatalysts.

Carbon materials have a very wide range of applications in the field of electrocatalysis, both as catalyst bodies and as excellent supports for catalysts. In this work, we obtained a graphitic-like orange-peel derived carbon (OPC) material through pre-carbonization and KOH activation strategies using discarded orange-peel as a raw material. OPC has good graphitization characteristics and a few-layer structure, making it very suitable as a support for nanoparticle catalysts. In order to compare the performance of OPC, we used commercial graphene as the benchmark, made two carbon materials uniformly loaded with ruthenium nanoparticles under the same conditions, and obtained two HER catalysts (Ru/OPC and Ru/rGO). The results indicate that Ru/OPC has excellent HER catalytic performance under alkaline conditions, not only superior to Ru/rGO, but also surpassing commercial Pt/C. In 1 M KOH; the overpotential of Ru/OPC is only 3 mV at -10 mA cm-2, greatly exceeding those of Ru/rGO (100 mV) and Pt/C (31 mV). Under high current density (j), the performance of Ru/OPC is even better; the overpotential is 79 mV and 136 mV at -100 mA cm-2 and -200 mA cm-2, respectively. More importantly, Ru/OPC also has a very high TOF and long-term stability, with a TOF of up to 10.62 H2 s-1 at an overpotential of 100 mV and almost no attenuation after 72 h of operation at -50 mA cm-2. Ru/OPC also exhibits good catalytic performance under acidic conditions, significantly superior to that of Ru/rGO. For Ru/OPC, the overpotential is 86 mV, 167 mV and 214 mV at -10 mA cm-2, -100 mA cm-2 and -200 mA cm-2, respectively. Under the same conditions, the overpotential of Ru/rGO is 143 mV, 253 mV and 306 mV at -10 mA cm-2, -100 mA cm-2 and -200 mA cm-2, respectively.

Ru@N/S/TiO2/rGO: a high performance HER electrocatalyst prepared by dye-sensitization.

Hydrogen production from water-splitting is one of the most promising hydrogen production methods, and the preparation of the hydrogen evolution reaction (HER) catalyst is very important. Although Pt-based materials have the best catalytic activity for HER, their high price and scarcity greatly limit their large-scale industrial application prospects. Herein, a new method to prepare HER catalyst is described, where dyes used in dye-sensitized solar cells (DSSCs) were used as precursors. A high performance HER catalyst (Ru@N/S/TiO2/rGO, Ru nanoparticles (NPs) supported on N/S-doped TiO2/rGO hybrids) was prepared, and the stereoscopic molecular structure of the porphyrin dye, JR1, not only provides a prerequisite for the preparation of the hyperdispersed Ru NPs, but also successfully realizes N/S co-doping. The Ru@N/S/TiO2/rGO shows an excellent catalytic performance for the HER, which is almost the same as that with Pt/C. In 0.5 M H2SO4, the overpotential is 60 mV at 10 mA cm-2, and the Tafel slope is only 51 mV dec-1. In 1 M KOH, the overpotential is only 5 mV at 10 mA cm-2, and the Tafel slope is only 45 mV dec-1, and this performance is much better than most of the HER catalysts that have been reported. When Ru@N/S/TiO2/rGO is utilized as a catalyst in an alkaline water electrolyzer, a bias of only 1.52 V is able to complement overall water-splitting at 10 mA cm-2 (1.78 V, 100 mA cm-2). The molecular structure and coordination metal species of the dyes are easy to adjust, and the the stereoscopic structure is very helpful for inhibiting the aggregation of the metal NPs, and the strong anchoring effect with TiO2 or other carbon materials is also very helpful to achieve heteroatom doping. In addition, the process of dye-sensitization is simple and repeatable, and is a novel and efficient method to prepare the electrocatalyst.

An Efficient Catalyst Derived from Carboxylated Lignin-Anchored Iron Nanoparticle Compounds for Carbon Monoxide Hydrogenation Application.

Catalytic activity and target product selectivity are strongly correlated to the size, crystallographic phase, and morphology of nanoparticles. In this study, waste lignin from paper pulp industry is employed as the carbon source, which is modified with carboxyl groups at the molecular level to facilitate anchoring of metals, and a new type of carbon-based catalyst was obtained after carbonization. As a result, the size of the metal particles is effectively controlled by the chelation between -COO- and Fe3+. Furthermore, Fe/CM-CL with a particle size of 1.5-2.5 nm shows excellent catalytic performance, the conversion of carbon monoxide reaches 82.3%, and the selectivity of methane reaches 73.2%.

Fe3O4-Loaded g-C3N4/C-Layered Composite as a Ternary Photocatalyst for Tetracycline Degradation.

A ternary photocatalyst, Fe3O4-loaded g-C3N4/C-layered composite (g-C3N4/C/Fe3O4) was fabricated by a facile sonication and in situ precipitation technique. Carbon nanosheets were prepared using the remaining non-metallic components of waste printed circuit boards as carbon sources. In this hybrid structure, g-C3N4 was immobilized on the surfaces of carbon nanosheets to form a layered composite, and 10-15 nm Fe3O4 nanoparticles are uniformly deposited on the surface of the composite material. The photocatalytic performance of the catalyst was studied by degrading tetracycline (TC) under simulated sunlight. The results showed that the photoactivity of the g-C3N4/C/Fe3O4 composite to TC was significantly enhanced, and the degradation rate was 10.07 times higher than that of pure g-C3N4, which was attributed to Fe3O4 nanoparticles and carbon nanosheets. Carbon sheets with good conductivity are an excellent electron transporter, which promotes the separation of photogenerated carriers and the Fe3O4 nanoparticles can utilize electrons effectively as a center of oxidation-reduction. Moreover, a possible photocatalytic mechanism for the excellent photocatalytic performance was proposed.

Self-Assembly by Coordination with Organic Antenna Chromophores for Dye-Sensitized Solar Cells.

The development of new sensitizers and new sensitization methods is one of the important means to enhance the conversion efficiency of dye-sensitized solar cells (DSSCs); the ultimate goal is to broaden the spectral response of dyes, reduce electron recombination, and suppress dye aggregation. In this study, we have developed a series of new self-assembled dyes and applied them in DSSCs. We prepared two organic antenna chromophores S1 and S2 and coordinated them with two acceptors A1 and A2 via zinc to construct A-Zn-S series self-assembled dyes. This method is very simple and feasible and can avoid the complex synthesis steps of traditional dyes; the results show that the light-harvesting ability of devices can be improved and charge recombination can be reduced by adjusting the structures of the antenna chromophores and acceptors. The device with A2-Zn-S1 gave a power conversion efficiency of 4.25%, which was higher than those with A1-Zn-S1 (3.88%), A1-Zn-S2 (3.21%), and A2-Zn-S2 (3.52%); the main reason for this is that the different coordination combinations between the antenna chromophore and the acceptor show great differences in Voc and Jsc. The device based on A2-Zn-S1 showed a high Voc of 632 mV and a high Jsc of 9.54 mA cm-2; one reason for this is that S1 has better spectral responsiveness and another reason is that A2 has better steric resistance that effectively reduces charge recombination. Besides, IR spectra indicate that these self-assembled dyes anchored on a TiO2 surface by bicarboxyl anchoring groups are also very beneficial for improving the performance of dyes.

Rhodium-Catalyzed Site-Selective ortho-C-H Activation: Enone Carbonyl Directed Hydroarylation of Maleimides.

Enone carbonyl directed 1,4-addition of ortho-C-H bond in chalcones to maleimides was developed under the catalysis of Rh(III). This reaction furnished a variety of chalcone-based pharmacologically useful 3-arylated succinimide derivatives in good yields with excellent selectivity.

A supramolecular assembly of metal-free organic dye with zinc porphyrin chromophore for dye-sensitized solar cells.

Two porphyrin chromophores, P1 and P2, were prepared and used as antenna units to coordinate with a metal-free organic dye, JH1, containing pyridine groups. This supramolecular self-assembly strategy can not only effectively improve the light-harvesting ability of the devices but also effectively reduces electron recombination by preventing I3- of the electrolyte from penetrating into the TiO2 surface. The DSSC based on JH1 showed a PCE of 2.46%, with a Voc of 615 mV, Jsc of 6.54 mA cm-2, and FF of 61.18%. After supramolecular self-assembly, the Jsc and Voc of the device were greatly improved. Specifically for the device based on JH1 + P2, the PCE reached 4.39%, which is about 78% greater than the PCE of the device based on JH1; this is mainly due to the Jsc increase of 2.85 mA cm-2 and the Voc increase of 93 mV. Compared to co-sensitization, supramolecular self-assembly does not require tedious optimization steps; thus, this may be a promising and convenient way to improve the overall performance of DSSCs.

Insight into the effects of modifying π-bridges on the performance of dye-sensitized solar cells containing triphenylamine dyes.

Herein we prepare four novel D-π-A dyes based on triphenylamine (ZHG1, ZHG2, ZHG3 and ZHG4) by modifying the π-bridges. Compared with ZHG1, the power conversion efficiency (PCE) of ZHG2 is improved to 6.1% after the introduction of ethynyl. But further extension of the conjugation of the π-bridges by introducing the chromophore 4,8-bis(n-octyloxy)-benzo[1,2-b:4,5-b']dithiophene (BDT) into ZHG3 conversely decreases the PCE to 4.6%. Improving the coplanarity by replacing cyclobenzene with thiophene in ZHG4 after introducing BDT further decreases the PCE of ZHG4 to 4.3%. Theoretical calculations indicate that the LUMOs of ZHG3 and ZHG4 were mainly delocalized over benzothiadiazole which is far from the anchoring groups. Cyclic voltammetry experiments indicate that the LUMO energy levels of ZHG3 and ZHG4 are lower than those of ZHG1 and ZHG2. Both of these results affect the ability to inject electrons into the TiO2 conduction band. X-ray photoelectron spectroscopy (XPS) analysis shows that the mean thickness of the dye coverage for ZHG1, ZHG2, ZHG3 and ZHG4 is 16 Å, 18 Å, 27 Å and 24 Å, respectively. So the tilt angle of the dye backbone anchored on the TiO2 film is in the order of ZHG1 > ZHG2 > ZHG4 > ZHG3, which is consistent with the dye coverage of the outermost TiO2 surfaces. This result indicates that the intermolecular π-π aggregation in ZHG3 and ZHG4 with overlong π-bridges is more serious compared with that in ZHG1 and ZHG2. Perhaps the above two factors are the reason that the PCEs of ZHG3 and ZHG4 are lower than those of ZHG1 and ZHG2. So it is very important to find a balance point between the electron injection ability, intermolecular π-π aggregation and the expansion of the light absorption range.

Three Highly Stable Cobalt MOFs Based on "Y"-Shaped Carboxylic Acid: Synthesis and Absorption of Anionic Dyes.

Three Co(II) metal-organic frameworks (MOFs) were synthesized employing a rational design approach. On the basis of the different structures of three complexes, we tested their absorption properties toward two anionic dyes. The absorption results indicate that not only uncoordinated functional groups in the structure play an important role in adsorbing capacity but also physical forces can affect absorbing ability. Water stability testing shows that three crystals display high stability in aqueous solutions with different pH values. To our delight, the framework integrity of three complexes can be well-retained even after absorbing dyes.

Effects of heterocycles containing different atoms as π-bridges on the performance of dye-sensitized solar cells.

Two new D-π-A zinc porphyrin dyes with thiophene and furan π-bridges have been synthesized and employed in dye-sensitized solar cells (DSSCs). Here, the triphenylamine (TPA) moiety was used as the electron donor, and the hexylthiophene chromophores were introduced onto the donor groups, which effectively extended the π-conjugation system. Although the two dyes had similar molecular structures, there was a significant difference between their optical and photoelectric properties. The EIS analysis suggested that the dye with the thiophene π-bridge had a lower charge recombination rate compared to the dye with the furan π-bridge. Based on their light-harvesting abilities, the power conversion efficiency (PCE) of dye JP-S was higher than that of dye JP-O. The JP-S-based DSSC showed a PCE of 5.84%, whereas the PCE of the JP-O-based DSSC was 4.68%. Moreover, using the dye TTR1 as a co-sensitizer made up for the poor absorption of porphyrin dyes in the 480-600 nm range and reduced the charge recombination. The JP-S + TTR1-based DSSCs showed a higher PCE of 6.71%, and the Jsc and Voc values of the device were both increased using this strategy.