Precisely Constructed Metal Sulfides with Localized Single-Atom Rhodium for Photocatalytic C-H Activation and Direct Methanol Coupling to Ethylene Glycol.

Although there are many studies on photocatalytic environmental remediation, hydrogen evolution, and chemical transformations, less success has been achieved for the synthesis of industrially important and largely demanded bulk chemicals using semiconductor photocatalysis, which holds great potential to drive unique chemical reactions that are difficult to implement by the conventional heterogeneous catalysis. The performance of semiconductors used for photochemical synthesis is, however, usually unsatisfactory due to limited efficiencies in light harvesting, charge-carrier separation, and surface reactions. The precise construction of heterogeneous photocatalysts to facilitate these processes is an attractive but challenging goal. Here, single-atom rhodium-doped metal sulfide nanorods composed of alternately stacked wurtzite/zinc-blende segments are successfully designed and fabricated, which demonstrate record-breaking efficiencies for visible light-driven preferential activation of C-H bond in methanol to form ethylene glycol (EG), a key bulk chemical used for the production of polyethylene terephthalate (PET) polymer. The wurtzite/zinc-blende heterojunctions lined regularly in one dimension accelerate the charge-carrier separation and migration. Single-atom rhodium selectively deposited onto the wurtzite segment with photogenerated holes accumulated facilitates methanol adsorption and C-H activation. The present work paves the way to harnessing photocatalysis for bulk chemical synthesis with structure-defined semiconductors.

Sulfonate-Assisted Surface Iodide Management for High-Performance Perovskite Solar Cells and Modules.

Owing to the ionic nature of lead halide perovskites, their halide-terminated surface is unstable under light-, thermal-, moisture-, or electric-field-driven stresses, resulting in the formation of unfavorable surface defects. As a result, nonradiative recombination generally occurs on perovskite films and deteriorates the efficiency, stability, and hysteresis performances of perovskite solar cells (PSCs). Here, a surface iodide management strategy was developed through the use of cesium sulfonate to stabilize the perovskite surface. It was found that the pristine surface of common perovskite was terminated with extra iodide, that is, with an I-/Pb2+ ratio larger than 3, explaining the origination of surface-related problems. Through post-treatment of perovskite films by cesium sulfonate, the extra iodide on the surface was facilely removed and the as-exposed Pb2+ cations were chelated with sulfonate anions while maintaining the original 3D perovskite structure. Such iodide replacement and lead chelating coordination on perovskite could reduce the commonly existing surface defects and nonradiative recombination, enabling assembled PSCs with an efficiency of 22.06% in 0.12 cm2 cells and 18.1% in 36 cm2 modules with high stability.

Sinter-resistant Rh nanoparticles supported on γ-Al2O3 nanosheets as an efficient catalyst for dry reforming of methane.

γ-Al2O3 nanosheet supported rhodium catalysts with Rh loadings between 0.05 and 2 wt% were prepared by the impregnation method and used for dry reforming of methane (DRM). It was found that Rh species on γ-Al2O3 nanosheets demonstrated excellent stability against sintering at high temperature. After calcining in air at 800 °C followed by reducing with hydrogen at 600 °C, the average particle size of Rh at maximum distribution increases from 1.0 ± 0.3 to 1.8 ± 0.3 nm with an increase in Rh loadings in the catalysts from 0.05 to 2 wt%. Even after reducing with hydrogen at 900 °C, the average size of Rh particles in the catalysts still remained below 2 nm. The results of catalytic performance evaluation show that CH4 and CO2 conversions of 84% and 90%, respectively, with a H2/CO ratio in syngas close to unity can be achieved with a catalyst of Rh loading of only 0.05 wt% at 750 °C. The performance of the catalyst remains stable for more than 200 h. No significant aggregation of the Rh particles is observed on the catalyst after the reaction. The results of XPS, H2-TPR and O2-TPD characterization methods indicate that the strong interaction between Rh and the γ-Al2O3 nanosheets plays a key role in increasing the dispersion of Rh species in the catalyst and preventing it from sintering under high temperature conditions. This factor is also responsible for the superior activity and stability of the catalyst with extremely low Rh loading for the DRM reaction.

Chemoselective Hydrogenation of Nitroaromatics at the Nanoscale Iron(III)-OH-Platinum Interface.

Catalytic hydrogenation of nitroaromatics is an environment-benign strategy to produce industrially important aniline intermediates. Herein, we report that Fe(OH)x deposition on Pt nanocrystals to give Fe(OH)x /Pt, enables the selective hydrogenation of nitro groups into amino groups without hydrogenating other functional groups on the aromatic ring. The unique catalytic behavior is identified to be associated with the FeIII -OH-Pt interfaces. While H2 activation occurs on exposed Pt atoms to ensure the high activity, the high selectivity towards the production of substituted aniline originates from the FeIII -OH-Pt interfaces. In situ IR, X-ray photoelectron spectroscopy (XPS), and isotope effect studies reveal that the Fe3+ /Fe2+ redox couple facilitates the hydrodeoxygenation of the -NO2 group during hydrogenation catalysis. Benefitting from FeIII -OH-Pt interfaces, the Fe(OH)x /Pt catalysts exhibit high catalytic performance towards a broad range of substituted nitroarenes.

Highly Dispersed Ni Catalyst on Metal-Organic Framework-Derived Porous Hydrous Zirconia for CO2 Methanation.

We report the preparation of porous hydrous zirconia by treatment of zirconium-based metal-organic framework (MOF) UiO-66 with a strong base. Microporosity of the original MOF was partially retained in the resultant porous hydrous zirconia. NiII centers were then adsorbed onto the OH-rich hydrous zirconia and in situ converted to highly dispersed Ni0 for CO2 hydrogenation to CH4. The activated catalyst after an induction period showed a turnover frequency of 345 h-1 or a space-time yield of 5851 mmol·gNi-1·h-1 with a CH4 selectivity of over 99%. The catalyst was tested for 100 h on stream, showing only a 4% decrease in activity, and was found to convert atmospheric CO2 to CH4 via CO2 collection through Na2CO3/NaHCO3 cycling. Thermal decomposition of NaHCO3 released CO2 for hydrogenation to CH4, and the resultant Na2CO3 absorbed CO2 from air to form NaHCO3. This work highlights the opportunity in using MOFs as precursors to prepare highly porous metal oxide/hydroxide supports for solid-gas phase catalysis.

Photoactivation of Cu Centers in Metal-Organic Frameworks for Selective CO2 Conversion to Ethanol.

CO2 hydrogenation to ethanol is of practical importance but poses a significant challenge due to the need of forming one C-C bond while keeping one C-O bond intact. CuI centers could selectively catalyze CO2-to-ethanol conversion, but the CuI catalytic sites were unstable under reaction conditions. Here we report the use of low-intensity light to generate CuI species in the cavities of a metal-organic framework (MOF) for catalytic CO2 hydrogenation to ethanol. X-ray photoelectron and transient absorption spectroscopies indicate the generation of CuI species via single-electron transfer from photoexcited [Ru(bpy)3]2+-based ligands on the MOF to CuII centers in the cavities and from Cu0 centers to the photoexcited [Ru(bpy)3]2+-based ligands. Upon light activation, this Cu-Ru-MOF hybrid selectively hydrogenates CO2 to EtOH with an activity of 9650 µmol gCu-1 h-1 under 2 MPa of H2/CO2 = 3:1 at 150 °C. Low-intensity light thus generates and stabilizes CuI species for sustained EtOH production.

Tuning of surface wettability of RGO-based aerogels for various adsorbates in water using different amino acids.

RGO-based aerogels with varied and controllable surface wettability were fabricated using different amino acids. Hydrophobic cys-RGO aerogels prepared by L-cysteine exhibited an outstanding adsorption toward oils and organic solvents, while hydrophilic lys-RGO aerogels obtained from L-lysine can be used as adsorbents for heavy metal ions in water.