A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol.

CO2 hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-OV-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kgcat-1·h-1 with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO2 with abundant oxygen vacancies can facilitate H2 dissociation energetically and thus improve CO2 hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

Boosting Low-Temperature CO2 Hydrogenation over Ni-based Catalysts by Tuning Strong Metal-Support Interactions.

Rational design of low-cost and efficient transition-metal catalysts for low-temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low-temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g-1 h-1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni-based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re-constructing monoclinic-ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal-support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.

Catalytic Decomposition Mechanism of PH3 on 3DCuO/C and High Value Utilization of Deactivated Catalysts.

With the widespread application of lithium iron phosphate batteries, the production capacity of the yellow phosphorus industry has increased sharply, and the treatment of the highly toxic by-product PH3 is facing severe challenges. In this study, a 3D copper-based catalyst (3DCuO/C) that can efficiently decompose PH3 at low temperatures and low oxygen concentrations is synthesized. The PH3 capacity is up to 181.41 mg g-1 , which is superior to that previously reported in the literature. Further studies indicated that the special 3D structure of 3DCuO/C induces oxygen vacancies on the surface of CuO, which is beneficial to the activation of O2 , and then promotes the adsorption and dissociation of PH3 . The doping of P after dissociation determines the formation of Cu-P, and the eventual conversion to Cu3 P leads to the deactivation of CuO active sites. More strikingly, due to the appearance of Cu3 P, the deactivated De-3DCuO/C (Cu3 P/C) exhibited significant activity in the photocatalytic degradation of rhodamine B and photocatalytic oxidation of Hg0 (gas) and can also be a candidate as an anode material for Li batteries after modification, which will provide a more thorough and economical treatment scheme for deactivated catalysts.

Enhanced adsorption of hydrophobic organic contaminants by high surface area porous graphene.

The relatively low surface area and micropore volume of graphene nanosheets (GNS) limit their potential application as effective adsorbents for hydrophobic organic contaminants (HOCs). In this study, KOH etching was used to develop activated GNS (K-GNS) for adsorption of model HOCs such as naphthalene, phenol, nitrobenzene, and bisphenol A. After activation, the specific surface area (SSA) of K-GNS increased to 885 m2/g, which was three times larger than that of GNS. The micropore volume of K-GNS substantially increased and the C/O ratio was doubled. Accordingly, the adsorption capacity of these HOCs on K-GNS was larger than that of pristine GNS (P-GNS) by 2-8 times. The kinetic data was fitted by the pseudo-second-order model, and the adsorption isotherms of HOCs on P-GNS and K-GNS were fitted by the Freundlich model. The desorption studies showed the K-GNS had a lower rate of release than P-GNS. The high adsorption of naphthalene, phenol, nitrobenzene, and bisphenol A on P-GNS and K-GNS is dominated by hydrophobic and π-π interactions. Additionally, the π-π EDA interaction and hydrogen bond between K-GNS and substituents cannot be ignored.

Co-contaminant effects on ofloxacin adsorption onto activated carbon, graphite, and humic acid.

Given their voluminous application, significant amounts of fluoroquinolones are discharged into the environment through wastewater effluent. Adsorption has been shown to be a critical process controlling the environmental behaviors of fluoroquinolones. Competition between ofloxacin (OFL) and naphthalene (NAP)/bisphenol A (BPA) and their adsorption on activated carbon (AC), graphite (GP), and humic acid (HA) were investigated. The suppressed adsorption of OFL was observed on AC and GP, but not on HA, by NAP or BPA. Moreover, for AC, the competition by NAP was slightly stronger than that by BPA. However, for GP, the competition with BPA was higher than that with NAP. These observations indicate that competitive adsorption of OFL with respect to NAP/BPA depends on the degree of overlap of adsorption sites, as interpreted by the following: (i) AC can provide overlapping adsorption sites for OFL, BPA, and NAP, which include non-specific adsorption sites, such as hydrophobic sites, π-π interactions, and micropore filling; (ii) π-π interactions and hydrogen bonding might be responsible for the strong competitive adsorption between BPA and OFL on GP; and (iii) OFL adsorbs on HA through specific adsorption force-electrostatic attraction, with which NAP and BPA cannot compete.