Tong Ding

Hydrogenated Cagelike Titania Hollow Spherical Photocatalysts for Hydrogen Evolution under Simulated Solar Light Irradiation

We synthesized the hydrogenated cagelike TiO2 hollow spheres through a facile sacrificial template method. After the hydrogenation treatment, the disordered surface layer and cagelike pores were generated on the shell of the hollow spheres. The spheres exhibit a high hydrogen evolution rate of 212.7 ± 10.6 μmol h(-1) (20 mg) under the simulated solar light irradiation, which is ∼12 times higher than the hydrogenated TiO2 solid spheres and is ∼9 times higher than the original TiO2 hollow spheres. The high activity results from the unique architectures and hydrogenation. Both the multiple reflection that was improved by the cagelike hollow structures and the red shift of the absorption edge that was induced by hydrogenation can enhance the ultraviolet and visible light absorption. In addition, the high concentration of oxygen vacancies, as well as the hydrogenated disordered surface layer, can improve the efficiency for migration and separation of generated charge carriers.

Confined small-sized cobalt catalysts stimulate carbon-chain growth reversely by modifying ASF law of Fischer–Tropsch synthesis

Fischer–Tropsch synthesis (FTS) is a promising technology to convert syngas derived from non-petroleum-based resources to valuable chemicals or fuels. Selectively producing target products will bring great economic benefits, but unfortunately it is theoretically limited by Anderson–Schulz–Flory (ASF) law. Herein, we synthesize size-uniformed cobalt nanocrystals embedded into mesoporous SiO2 supports, which is likely the structure of water-melon seeds inside pulps. We successfully tune the selectivity of products from diesel-range hydrocarbons (66.2%) to gasoline-range hydrocarbons (62.4%) by controlling the crystallite sizes of confined cobalt from 7.2 to 11.4 nm, and modify the ASF law. Generally, larger Co crystallites increase carbon-chain growth, producing heavier hydrocarbons. But here, we interestingly observe a reverse phenomenon: the uniformly small-sized cobalt crystallites can strongly adsorb active C* species, and the confined structure will inhibit aggregation of cobalt crystallites and escape of reaction intermediates in FTS, inducing the higher selectivity towards heavier hydrocarbons.Fischer–Tropsch synthesis (FTS) is theoretically limited by Anderson–Schulz–Flory (ASF) law. Here, the authors successfully tune the selectivity of products from diesel-range hydrocarbons to gasoline-range hydrocarbons in FTS by controlling the crystallite sizes of confined cobalt, and modify the ASF law.

Insight into Copper Oxide-Tin Oxide Catalysts for the Catalytic Oxidation of Carbon Monoxide: Identification of Active Copper Species and a Reaction Mechanism

Herein, we report the high activity of CuO‐SnO2 catalysts for the catalytic oxidation of CO. In particular, SnCu30 shows the highest activity and a high water resistance. If we compare the XRD, X‐ray absorption fine structure, and H2 temperature‐programmed reduction results of SnCu30 before and after HNO3 treatment, we find the existence of three kinds of Cu species in the catalyst, that is, highly dispersed CuO, bulk CuO, and Cu incorporated in the SnO2 lattice. The highly dispersed CuO and the surface lattice oxygen species are the active sites for the catalytic oxidation of CO. We used X‐ray photoelectron spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy to confirm the existence of Cu+ species on the surface of the CuO‐SnO2 catalysts, which can provide the adsorption sites for CO. Our results show that the reaction pathways of the catalytic oxidation of CO over the CuO‐SnO2 catalysts follow the Mars–van Krevelen model.

Dimethyl ether steam reforming to produce H2 over Ga-doped ZnO/γ-Al2O3 catalysts

Herein, we report the performance of a series of gallium-doped zinc oxide (GDZ) catalysts mechanically mixed with γ-Al2O3 (GDZ/γ-Al2O3) for the dimethyl ether (DME) steam reforming (SR) to produce H2. Compared with the ZnO catalyst mechanically mixed with γ-Al2O3, the doping of ZnO with gallium can significantly improve the conversion of DME and the yield of hydrogen. The catalyst with a Zn : Ga molar ratio of 9 : 1 has the highest conversion of DME (95.4%) and yield of hydrogen (95.0%) at 450 °C. The carbon dioxide selectivity of GDZ/γ-Al2O3 catalysts is higher than 95%, which is much higher than that of the CuZnAlO/γ-Al2O3 catalyst. Moreover, the GDZ/γ-Al2O3 catalysts have better stability than the CuZnAlO/γ-Al2O3 catalyst. Doping of ZnO with gallium generates a large number of oxygen vacancies on the catalyst, which is beneficial to the DME SR reaction. Our results indicate that HCOO– is an intermedium of DME SR over GDZ/γ-Al2O3 catalysts, and the transformation from HCOO– to CO2 is the rate-controlling step. The results of conductivity indicate that the rate-controlling step is an n-type reaction.

Alloy‐Mediated Ultra‐Low CO Selectivity for Steam Reforming over Cu−Ni Bimetallic Catalysts

Steam reforming of simple oxygenated hydrocarbons without C−C bonds is suitable for small‐scale decentralized H2 production for fuel cells. However, the relatively high CO concentration in H2‐rich reformates produced by traditional Cu‐based catalysts will poison the Pt‐based anode in fuel cells. Here, we describe a new approach to the design of Cu−Ni bimetallic catalysts based on nickel‐phyllosilicate for steam reforming of dimethyl ether (DME). With the tunable formation of the Cu−Ni alloy, we can modulate the selectivity of CO and CH4 in steam reforming and achieve H2‐rich reformates with an ultra‐low concentration of CO (below 1000 ppm). This process only requires simple and low‐energy purification pretreatments to meet the requirements of commercial fuel cells. Mechanistic studies reveal that the Cu−Ni alloy can adsorb CO, particularly at high temperatures, and simultaneously suppress CO dissociation to methane.

Modification of Cu/SiO2 Catalysts by La2O3 to Quantitatively Tune Cu+-Cu0 Dual Sites with Improved Catalytic Activities and Stabilities for Dimethyl Ether Steam Reforming

Dimethyl ether steam reforming (DME SR) is a promising route to provide H2 for on‐board H2‐based fuel cells. Herein, we synthesized the La2O3‐modified Cu/SiO2 catalyst with dual copper species of Cu0 and Cu+ for DME SR, which exhibits both the high catalytic performance and long‐term stability. The strong electron donor‐acceptor interaction between the lanthanum and copper species occurs after reduction of the catalysts, which is an essential factor to quantitatively determine the ratio of Cu+/(Cu0+Cu+). The addition of La can improve the dispersion of both metallic Cu and Cu2O on the catalysts, as well. After modulating the ratio of Cu+/(Cu0+Cu+) to ∼0.5 by varying the La loading, we achieved the highest activity and lowest CO selectivity. After the durability tests, the results of TEM, EXAFS, and XPS reveal that the addition of La on the Cu/SiO2 catalysts not only stabilizes the copper species from aggregation, especially for the metallic Cu, but also avoids over‐reduction of the Cu+ species to Cu0. The constant ratio of Cu+/(Cu0+Cu+) on the La‐modified Cu/SiO2 catalyst ensures the high catalytic stability in DME SR.

Engineering surface defects and metal–support interactions on Pt/TiO2(B) nanobelts to boost the catalytic oxidation of CO

Herein, we report the high performance of thermally reduced Pt/TiO2(B) catalysts for the catalytic oxidation of CO. Our findings show that through hydrogen spillover from Pt to TiO2, surface-engineered defects of oxygen vacancies are “constructed” on the TiO2 support during the reduction process, thus generating active surface-adsorbed oxygen species. With an increase of the reduction temperature, the TiO2(B) phase gradually transforms to the anatase phase, which takes place from the bulk to the surface of TiO2, and is eventually completed at 700 °C. Compared with the anatase phase, the oxygen vacancies are more easily formed on the TiO2(B) phase, and the latter has much stronger interactions with Pt, as well. As the reduction temperature increases, the metal–support interaction between Pt and TiO2(B) is strengthened. Meanwhile, we simultaneously observe an increase in the dispersion of Pt, the proportion of Pt0 and the adsorbed oxygen species on the surface. Our findings reveal that for thermally reduced Pt/TiO2 catalysts, surface-adsorbed oxygen and Pt0 are active species for the catalytic oxidation of CO. Among the thermally reduced catalysts, H-600 shows the highest catalytic activity because it has the largest amount of active Pt0 sites and surface-adsorbed oxygen species. In addition, it shows high water vapor resistance.

Enhanced activity of CuO/K2CO3/MgAl2O4 catalyst for lean NOx storage and reduction at high temperatures

Herein, we designed a new NOx storage and reduction CuO/K2CO3/MgAl2O4 catalyst operating within the high temperature region of 350–550 °C. Compared with the Al2O3 supported catalyst with the same Cu and K loading, it exhibits superior NOx storage and reduction performance. The NOx reduction percentage (NRP) of the CuO/K2CO3/MgAl2O4 catalyst remains above 90% over a wide temperature range (400–550 °C), and reaches the highest NRP of 99.9% at 450 °C with the N2 selectivity of 99.7%. Uncovered CuO particles with better reducibility exist on the CuO/K2CO3/MgAl2O4 catalyst, with the high NOx oxidation and reduction ability above 400 °C. Potassium carbonates on the CuO/K2CO3/MgAl2O4 catalyst mainly exist in three forms, including free ionic carbonate, bridging bidentate carbonate and chelating bidentate carbonate. Under lean-burn conditions, most of carbonates on the CuO/K2CO3/MgAl2O4 catalyst can store NOx to form nitrates, but only parts of them participate in NOx storage on the CuO/K2CO3/Al2O3 catalyst. The MgAl2O4 support offers additional sites for NOx adsorption, while the formed nitrate on it shows low thermal stability. So, NOx is mainly stored on K2CO3 at high temperatures, because MgAl2O4 can enhance the thermal stability of the supported K2CO3 on it. Our results show that the thermal stability of K2CO3 directly determines the thermal stability of the formed nitrates. Accordingly, the CuO/K2CO3/MgAl2O4 catalyst shows the high NSR activity because of the efficient redox ability of CuO and high thermal stability of K2CO3 at high operating temperatures.