Electrocatalytic CO2 Upgrading to Triethanolamine by Bromine-Assisted C2 H4 Oxidation.

The electrocatalytic carbon dioxide (CO2 ) reduction is a promising approach for converting this greenhouse gas into value-added chemicals, while the capability of producing products with longer carbon chains (Cn >3) is limited. Herein, we demonstrate the Br-assisted electrocatalytic oxidation of ethylene (C2 H4 ), a major CO2 electroreduction product, into 2-bromoethanol by electro-generated bromine on metal phthalocyanine catalysts. Due to the preferential formation of Br2 over *O or Cl2 to activate the C=C bond, a high partial current density of producing 2-bromoethanol (46.6 mA⋅cm-2 ) was obtained with 87.2 % Faradaic efficiency. Further coupling with the electrocatalytic nitrite reduction to ammonia at the cathode allowed the production of triethanolamine with six carbon atoms. Moreover, by coupling a CO2 electrolysis cell for in situ C2 H4 generation and a C2 H4 oxidation/nitrite reduction cell, the capability of upgrading of CO2 and nitrite into triethanolamine was demonstrated.

Boosting Selective Oxidation of Ethylene to Ethylene Glycol Assisted by In situ Generated H2 O2 from O2 Electroreduction.

Ethylene glycol is a useful organic compound and chemical intermediate for manufacturing various commodity chemicals of industrial importance. Nevertheless, the production of ethylene glycol in a green and safe manner is still a long-standing challenge. Here, we established an integrated, efficient pathway for oxidizing ethylene into ethylene glycol. Mesoporous carbon catalyst produces H2 O2 , and titanium silicalite-1 catalyst would subsequently oxidize ethylene into ethylene glycol with the in situ generated H2 O2 . This tandem route presents a remarkable activity, i.e., 86 % H2 O2 conversion with 99 % ethylene glycol selectivity and 51.48 mmol gecat -1 h-1 production rate at 0.4 V vs. reversible hydrogen electrode. Apart from generated H2 O2 as an oxidant, there exists ⋅OOH intermediate which could omit the step of absorbing and dissociating H2 O2 over titanium silicalite-1, showing faster reaction kinetics compared to the ex situ one. This work not only provides a new idea for yielding ethylene glycol but also demonstrates the superior of in situ generated H2 O2 in tandem route.

Co-adsorption of O2 and C2H4 on a Free Gold Dimer Probed via Infrared Photodissociation Spectroscopy.

Infrared multiple photon dissociation (IR-MPD) spectroscopy in conjunction with density functional theory (DFT) calculations has been employed to study the activation of molecular oxygen and ethylene co-adsorbed on a free gold dimer cation Au2+. Both studied complexes, Au2O2(C2H4)+ and Au2O2(C2H4)2+, show distinct features of both intact O2 and ethylene co-adsorbed on the cluster. However, the ethylene C=C double bond is activated, increasing in length by up to 0.07 Å compared with the free molecule, and the red shift of the O-O vibration frequency increases with the number of adsorbed ethylene molecules, indicating a small but increasing activation of the O-O bond. The small O2 activation and the rather weak interaction between O2 and C2H4 are also reflected in the calculated electronic structure of the co-adsorption complexes which shows only a small occupation of the empty anti-bonding O2 2π*2p orbital as well as the localization of most of the Kohn-Sham orbitals on O2 and C2H4, respectively, with only limited mixing between O2 and C2H4 orbitals. The results are compared with theoretical studies on neutral AuxO2(C2H4) (x = 3, 5, 7, 9) complexes.

Photocatalytic Abatement of Volatile Organic Compounds by TiO2 Nanoparticles Doped with Either Phosphorous or Zirconium.

The aim of this work is to study the activity of novel TiO2-based photocatalysts doped with either phosphorus or zirconium under a UV-Vis source. A set of mesoporous catalysts was prepared by the direct synthesis: TiO2_A and TiO2_B (titanium oxide synthesized by two different procedures), P-TiO2 and Zr-TiO2 (binary oxides with either nonmetal or metal into the TiO2 framework). Complementary characterizations (N2 physisorption at 77 K, X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) analysis, X-ray Photoelectron Spectroscopy (XPS), and (DR)UV-Vis spectroscopy) were used to investigate the physicochemical properties of the prepared catalysts. Then, the photocatalysts were tested for the oxidation of propylene and ethylene under UV-Vis light. As a result, the most promising catalyst for both the propylene and ethylene oxidation reactions was the P-TiO2 (propylene conversion = 27.8% and ethylene conversion = 13%, TOS = 3 h), thus confirming the beneficial effect of P-doping into the TiO2 framework on the photocatalytic activity.

Defective, Porous TiO2 Nanosheets with Pt Decoration as an Efficient Photocatalyst for Ethylene Oxidation Synthesized by a C3N4 Templating Method.

We report herein a C3N4 templating method for successfully synthesizing defective, porous TiO2 nanosheets with Pt decoration as an efficient photocatalyst for C2H4 oxidation. During the synthetic procedure, C3N4 not only acts as a 2D template to direct synthesize porous TiO2 nanosheets (TiO2-NS) but also facilitates oxygen vacancy formation on TiO2. The resultant TiO2-NS shows enhanced UV and visible-light photoactivities toward C2H4 oxidation as compared to blank TiO2 (TiO2-B) prepared without C3N4 template. Subsquently, Pt nanoparticles are homogeneously decorated onto the surface of TiO2-NS. The as-obtained Pt-TiO2-NS exhibits efficient photocatalytic activity and stability toward ethylene oxidation.