Adsorption and activation of small molecules on boron nitride catalysts.

Hexagonal boron nitride possesses a unique layered structure, high specific surface area and similar electronic properties as graphene, which makes it not only a promising catalyst support, but also a highly effective metal-free catalyst in the booming field of green chemistry. Reactions involving small molecules (e.g., oxygen, low carbon alkanes, nitrogen and carbon dioxide) have always been a hot topic in catalytic research, especially associated with the adsorption and activation regime of different forms of small molecules on catalysts. In this review, we have investigated the adsorption of different small molecules and the relevant activation mechanisms of four typical chemical bonds (OO, C-H, NN, CO) on hexagonal boron nitride. Recent progress on approaches adopted to enhance the activation capacity such as doping, defect engineering and heterostructuring are summarized, highlighting the potential applications of nonmetallic hexagonal boron nitride catalysts in various reactions. This comprehensive investigation offers a reference point for the enhanced mechanistic understanding and future design of effective and sustainable catalytic systems based on boron nitride.

Trace CO elimination in H2-rich streams with a wide operation temperature window: Co deposited CuO-CeO2 catalysts.

This work provides a new strategy to eliminate trace CO in H2-rich gas in a wide operation temperature window for the application of hydrogen fuel cells. We engineered Co deposited CuO-CeO2 catalysts with a Co/(Cu + Ce) molar ratio of 1/1 that manages to maintain the CO level at below 100 ppm from 85 to 240 °C in the H2-rich reformate stream. CO-PROX and CO methanation reaction respectively occurred in the low and high temperature ranges. Multiple characterization techniques demonstrate that the molar ratio of Co/(Cu + Ce) significantly affects the synergistic interactions between the Cu, Co and Ce species, and ultimately the CO oxidation and CO methanation reactions. At low reaction temperatures, the Cu-Ce interaction mainly dominates the CO-PROX process, while at high reaction temperatures, CO methanation reaction takes place due to the reduction of Co3O4 to Co0 and the Co-Ce interaction takes charge of the CO methanation. Moreover, the increment of Co/(Cu + Ce) from 1/2 to 1 gives rise to the reprecipitation of the partially dissolved Cu species on Co3O4, which strengthens the Cu-Co interaction and stabilizes surface Cu+ and Co3+, thus promoting the low temperature CO-PROX catalytic performance.

Elucidating the structure, redox properties and active entities of high-temperature thermally aged CuOx-CeO2 catalysts for CO-PROX.

CuOx-CeO2 catalysts with different copper contents are synthesized via a coprecipitation method and thermally treated at 700 °C. Various characterization techniques including X-ray diffraction (XRD) Rietveld refinement, N2 adsorption-desorption isotherms, X-ray photoelectron spectra (XPS), UV-Raman, high-resolution transmission electron microscopy (HRTEM), temperature-programmed reduction (TPR) and in situ diffuse reflectance infrared Fourier transform spectra (DRIFTs) were adopted to investigate the structure/texture properties, oxygen vacancies, Cu-Ce interaction and redox properties of the catalysts. After the thermal treatment, the catalysts exhibited outstanding catalytic properties for the preferential oxidation (PROX) of CO (with the T50% of 62 °C and the widest operation temperature window of 85-140 °C), which provided a new strategy for the design of Cu-Ce based catalysts with high catalytic performance. The characterization results indicated that moderately elevating the copper content (below 5%) increases the amount of highly dispersed Cu species in the catalysts, including highly dispersed surface CuOx species and strongly bonded Cu-[Ox]-Ce species, strengthening the Cu-Ce interaction, increasing oxygen vacancies and promoting redox properties, but a further increase in copper content causes the agglomeration of crystalline CuO and decreases the highly dispersed Cu species. This work also provides evidence from the perspective that the catalytic performance of CuOx-CeO2 catalysts for CO-PROX at low and high reaction temperatures is dependent on the redox properties of highly dispersed CuOx species and strongly bonded Cu-[Ox]-Ce species, respectively.

Doping effect of transition metals (Zr, Mn, Ti and Ni) on well-shaped CuO/CeO2(rods): nano/micro structure and catalytic performance for selective oxidation of CO in excess H2.

A series of CuO/CeM(rod) catalysts doped by transition metals were prepared and systematically characterized. The introduction of Mn and Ti plays a significant role in promoting the catalytic performance of the CuO/CeO2(rod) catalyst for the preferential oxidation of CO in H2-rich gas, while the doping with Zr basically maintains the same catalytic activity and Ni leads to a negative influence. Mn and Ti additives remarkably enrich the formation of defect structures and promote copper ion incorporation into the surface of CeM(rod), which greatly facilitates the generation of strong interfacial copper-ceria interaction in CuO/CeMn(rod) and CuO/CeTi(rod). In addition, CuO/CeMn(rod) possesses excellent surface oxygen mobility at low temperature due to the existence of manganese species with multiple valence states and todorokite species. The Ce-doped perovskite structure (Na0.5Ce0.5TiO3) further adjusts the oxygen vacancy in CuO/CeTi(rod) and anchors copper oxide species with strong interactions. Although a homogeneous solid solution is formed in CeZr(rod) with increased amounts of oxygen vacancies, the interaction between copper and ceria species in the interface of CuO/CeZr(rod) remains the same as with CuO/CeO2(rod). The addition of Ni impairs the dispersion of copper oxide and weakens the copper-ceria interaction, which damages the catalytic performance of CuO/CeNi(rod).