ZrO₂ nanoparticles, ZrO₂ (P) and ZrO₂ (H), with different tetragonal phase contents, were prepared. ZrO₂ (P) possessed higher tetragonal phase content than ZrO₂ (H). Ni/ZrO₂ catalysts (10% (w/w)), using ZrO₂ (P) and ZrO₂ (H) as supports, were prepared using an impregnation method, and were characterized using XRD, Raman, H₂-TPR, XPS, and H₂-TPD techniques. Their catalytic performance in maleic anhydride hydrogenation was tested. The Ni/ZrO₂ (P) catalyst exhibited stronger metal-support interactions than the Ni/ZrO₂ (H) catalyst because of its higher number of oxygen vacancies and the low-coordinated oxygen ions on its surface. Consequently, smaller Ni crystallites and a higher C=C hydrogenation activity for maleic anhydride to succinic anhydride were obtained over a Ni/ZrO₂ (P) catalyst. However, the C=O hydrogenation activity of Ni/ZrO₂ (P) catalyst was much lower than that of the Ni/ZrO₂ (H) catalyst. A 43.5% yield of γ-butyrolacetone was obtained over the Ni/ZrO₂ (H) catalyst at 210 °C and 5 MPa of H₂ pressure, while the yield of γ-butyrolactone was only 2.8% over the Ni/ZrO₂ (P) catalyst under the same reaction conditions. In situ FT-IR characterization demonstrated that the high C=O hydrogenation activity for the Ni/ZrO₂ (H) catalyst could be attributed to the surface synergy between active metallic nickel species and relatively electron-deficient oxygen vacancies.

A Cu-based nano-catalyst has been widely used in the ethynylation of formaldehyde; however, the effects of the presence of Cu on the reaction have not yet been reported. CuO/SiO₂ catalysts with different Cu species were prepared by impregnation (IM), deposition–precipitation (DP), and ammonia evaporation (AE). The structural evolution of the Cu species in different states of the ethynylation reaction and the structure–activity relationship between the existence state of the Cu species and the catalytic properties of the ethynylation reaction were studied. The results show that the Cu species in the CuO/SiO₂ (IM), prepared using the impregnation method, are in the form of bulk CuO, with large particles and no interactions with the support. The bulk CuO species are transformed into Cu⁺ with a low exposure surface at the beginning of the reaction, which is easily lost. Thus, this approach shows the lowest initial activity and poor cycle stability. A high dispersion of CuO and copper phyllosilicate exists in CuO/SiO₂ (DP). The former makes the catalyst have the best initial activity, while the latter slows release, maintaining the stability of the catalyst. There is mainly copper phyllosilicate in CuO/SiO₂ (AE), which is slowly transformed into a highly dispersed and stable Cu⁺ center in the in situ reaction. Although the initial activity of the catalyst is not optimal, it has the optimal service stability.

The proper selection of transition metals and support is pivotal to the design of active and selective catalysts for maleic anhydride hydrogenation (MAH). Herein, the M/CeO_2−δ (M = Co, Ni, Cu, respectively) catalysts with pre-optimised metal loading of 10 wt % were prepared via a wet impregnation method and well characterized to corroborate their MAH performance with the properties of metal, support and the M/CeO_2−δ catalysts. The results revealed that the metal dispersion on the catalyst declines in the order of Ni/CeO_2−δ > Co/CeO_2−δ > Cu/CeO_2−δ, similar to the apparent activity for maleic anhydride (MA) transformation to succinic anhydride (SA). The hydrogenolysis of SA to γ-butyrolactone (GBL) occurs on Ni/CeO_2−δ and Co/CeO_2−δ only when the MA → SA transformation completing. The Ni/CeO_2−δ displays superior activity and selectivity to Co/CeO_2−δ in both MA → SA and SA → GBL reactions, while the Cu/CeO_2−δ and CeO_2−δ are both inert for SA → GBL hydrogenolysis. The MA hydrogenation to SA follows the first order kinetic law on the Ni/CeO_2−δ and Co/CeO_2−δ catalysts yet a more complex kinetic characteristics observed on the Cu/CeO_2−δ. The distinct catalytic hydrogenation behaviours of the M/CeO_2−δ catalysts are assigned to the synergism of dispersion and electronic configuration of the transition metals and oxygen vacancies.

Through use of the hydrothermal technique, various shaped CeO₂ supports, such as nanocubes (CeO₂-C), nanorods (CeO₂-R), and nanoparticles (CeO₂-P), were synthesized and employed for supporting Ni species as catalysts for a maleic anhydride hydrogenation (MAH) reaction. The achievements of this characterization illustrate that Ni atoms are capable of being incorporated into crystal lattices and can occupy the vacant sites on the CeO₂ surface, which leads to an enhancement of oxygen vacancies. The results of the MAH reaction show that the morphology and shape of CeO₂ play an important role in the catalytic performance of the MAH reaction. The catalyst for the rod-like CeO₂-R obtains a higher catalytic activity than the other two catalysts. It can be concluded that the higher catalytic performances of rod-like CeO₂-R sample should be attributed to the higher dispersion of Ni particles, stronger support-metal interaction, more oxygen vacancies, and the lattice oxygen mobility. The research on the performances of morphology-dependent Ni/CeO₂ catalysts as well as the relative reaction strategy of MAH will be remarkably advantageous for developing novel catalysts for MA hydrogenation.

Supported metal catalysts are widely used in industrial processes, and the particle size of the active metal plays a key role in determining the catalytic activity. Herein, CeO₂-supported Ni catalysts with different Ni loading and particle size were prepared by the impregnation method, and the hydrogenation performance of maleic anhydride (MA) over the Ni/CeO₂ catalysts was investigated deeply. It was found that changes in Ni loading causes changes in metal particle size and active sites, which significantly affected the conversion and selectivity of MAH reaction. The conversion of MA reached the maximum at about 17.5 Ni loading compared with other contents of Ni loading because of its proper particle size and active sites. In addition, the effects of Ni grain size, surface oxygen vacancy, and Ni–CeO₂ interaction on MAH were investigated in detail, and the possible mechanism for MAH over Ni/CeO₂ catalysts was deduced. This work greatly deepens the fundamental understanding of Ni loading and size regimes over Ni/CeO₂ catalysts for the hydrogenation of MA and provides a theoretical and experimental basis for the preparation of high-activity catalysts for MAH.

Composite nanomaterials have been widely used in catalysis because of their attractive properties and various functions. Among them, the preparation of composite nanomaterials by redox has attracted much attention. In this work, pure Cu₂O was prepared by liquid phase reduction with Cu(NO₃)₂ as the copper source, NaOH as a precipitator, and sodium ascorbate as the reductant. With Fe(NO₃)₃ as the iron source and solid-state phase reaction between Fe³⁺ and Cu₂O, Cu_xO-Fe_yO_z nanocatalysts with different Fe/Cu ratios were prepared. The effects of the Fe/Cu ratio on the structure of Cu_xO-Fe_yO_z nanocatalysts were studied by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet confocal Raman (Raman), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS, XAES), and hydrogen temperature-programmed reduction (H₂-TPR). Furthermore, the structure–activity relationship between the structure of Cu_xO-Fe_yO_z nanocatalysts and the performance of formaldehyde ethynylation was discussed. The results show that Fe³⁺ deposited preferentially on the edges and corners of the Cu₂O surface, and a redox reaction between Fe³⁺ and Cu⁺ occurred, forming Cu_xO-Fe_yO_z nanoparticles containing Cu⁺, Cu²⁺, Fe²⁺, and Fe³⁺. With the increase of the Fe/Cu ratio, the content of Cu_xO-Fe_yO_z increased. When the Fe/Cu ratio reached 0.8, a core–shell structure with Cu₂O inside and a Cu_xO-Fe_yO_z coating on the outside was formed. Because of the large physical surface area and the heterogeneous structure formed by Cu_xO-Fe_yO_z, the formation of nonactive Cu metal is inhibited, and the most active species of Cu⁺ are exposed on the surface, showing the best formaldehyde ethynylation activity.