Mechanistic insights into NO‒H2 reaction over Pt/boron-doped graphene catalyst.

This work presents a systematical experimental and density functional theory (DFT) studies to reveal the mechanism of NO reduction by H2 reaction over platinum nanoparticles (NPs) deposited on boron-doped graphene (denoted as Pt/BG) catalyst. Both characterizations and DFT calculations identified boron (in Pt/BG) as an additional NO adsorption site other than the widely recognized Pt NPs. Moreover, BG led to a decrease of Pt NPs size in Pt/BG, which facilitated hydrogen spillover. The mathematical and physical criteria of the Langmuir-Hinshelwood dual-site kinetic model over the Pt/BG were satisfied, indicating that adsorbed NO on boron (in Pt/BG) was further activated by H-spillover. On the other hand, Pt/graphene (Pt/Gr) demonstrated a typical Langmuir-Hinshelwood single-site mechanism where Pt NPs solely served as active sites for NO adsorption. This work helps understand NO-H2 reaction over Pt/BG and Pt/Gr catalysts in a closely mechanistic view and provides new insights into roles of active sites for improving the design of catalysts for NO abatement.

Boron-doped graphene nanosheet-supported Pt: a highly active and selective catalyst for low temperature H2-SCR.

A series of boron-doped graphene-supported Pt (Pt/BG) nanosheets were designed and synthesized using a one-step facile hydrothermal method. ICP, XPS, and TPD results confirmed that boron atoms were successfully embedded into the graphene matrix. The selective catalytic reduction of nitric oxide with hydrogen (H2-SCR) was tested over Pt/BG catalysts. The multi-roles of doped-boron were investigated by Raman, BET, CO-chemisorption, H2-TPD, XPS, and NO-TPD. Boron doping led to a higher dispersion and smaller size of Pt nanoparticles, facilitated hydrogen spillover, promoted more metallic Pt formation, and increased both H2 and NO chemisorption, which were attributed to an enhanced Pt nucleation rate over doped-boron, electron donation from boron to Pt, and extra chemisorption sites. The reaction performances (conversion 94.7%, selectivity 90.3%, and TOF 0.092 s-1) were greatly promoted attributing to a bifunctional catalytic mechanism. This work paves the way to modify the structure and tune the chemisorption ability of graphene-based catalysts, and provides novel insights for designing high performance catalysts.

Significant Enhancement of Photocatalytic Reduction of CO2 with H2O over ZnO by the Formation of Basic Zinc Carbonate.

Electron-hole pair separation efficiency and adsorption performance of photocatalysts to CO2 are the two key factors affecting the performance of photocatalytic CO2 reduction with H2O. Distinct from conventional promoter addition, this study proposed a novel approach to address these two issues by tuning the own surface features of semiconductor photocatalyst. Three ZnO samples with different morphologies, surface area, and defect content were fabricated by varying preparation methods, characterized by XRD, TEM, and room-temperature PL spectra, and tested in photoreduction of CO2 with H2O. The results show that the as-prepared porous ZnO nanosheets exhibit a much higher activity for photoreduction of CO2 with H2O when compared to ZnO nanoparticles and nanorods attributed to the existence of more defect sites, that is, zinc and oxygen vacancies. These defects would lower the combination rate of electron-hole pair as well as promote the formation of basic zinc carbonate by Lewis acid-base interaction, which is the active intermediate species for photoreduction of CO2. ZnO nanoparticles and ZnO nanorods with few defects show weak adsorption for CO2 leading to the inferior photocatalytic activities. This work provides new insight on the CO2 activation under light irradiation.

Enhancement of Nitrite Reduction Kinetics on Electrospun Pd-Carbon Nanomaterial Catalysts for Water Purification.

We report a facile synthesis method for carbon nanofiber (CNF) supported Pd catalysts via one-pot electrospinning and their application for nitrite hydrogenation. A mixture of Pd acetylacetonate (Pd(acac)2), polyacrylonitrile (PAN), and nonfunctionalized multiwalled carbon nanotubes (MWCNTs) was electrospun and thermally treated to produce Pd/CNF-MWCNT catalysts. The addition of MWCNTs with a mass loading of 1.0-2.5 wt % (to PAN) significantly improved nitrite reduction activity compared to the catalyst without MWCNT addition. The results of CO chemisorption confirmed that the addition of MWCNTs increased Pd exposure on CNFs and hence improved catalytic activity.