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CO2 oxidative dehydrogenation of propane (CO2-ODHP), being not only favorable for olefin production but also beneficial for CO2 emission control, has recently attracted great attention. Here, a series of single metal (Cr) and bimetal (Zr, La, Fe) modified ZSM-5 zeolites were prepared via an impregnation method. It was found that the bimetal modified ZSM-5 possessed much higher C3H8 and CO2 conversion than that of monometallic modified Cr3%-ZSM-5 (Cr3%-Z5), especially for Cr3%Zr2%-ZSM-5 (Cr3%Zr2%-Z5), which displayed the highest activity (65.4%) and olefin yield (1.65 × 103 μmol·gcat−1 h−1). Various characterizations were performed, including XRD, N2 adsorption-desorption, H2-TPR, Raman, XPS, HAAD-STEM, and TEM. It was revealed that Zr not only favored an improvement in the redox ability of Cr, but also contributed to the surface dispersion of loaded Cr species, constituting two major reasons explaining the superior activity of Cr3%Zr2%-Z5. To further improve CO2-ODHP catalytic behavior, a series of Cr3%-ZSM-5@SBA-15-n composite zeolite catalysts with diverse (ZSM-5/SBA-15) mass ratios were prepared (Cr3%-ZS-n, n = 0.5, 2, 6, 16), which screened out an optimum mass ratio of six. Based on this, the Cr3%Zr2%-ZS-6 compound was further prepared, and it eventually achieved even higher CO2-ODHP activity (76.9%) and olefin yield (1.72 × 103 μmol·gcat−1 h−1). Finally, the CO2-ODHP reaction mechanism was further investigated using in situ FTIR, and it was found that the reaction followed the Mars–van Krevelen mechanism, wherein CO2 participated in the reaction through generation of polydentate carbonates. The Cr6+ constituted as the active site, which was reduced to Cr3+ after the dihydrogen reaction, and was then further oxidized into Cr6+ by CO2, forming polydentate carbonates, and thus cycling the reactive species Cr6+. Additionally, assisted by a Brönsted acid site (favoring breaking of the C-C bond), C2H4 and CH4 were produced.

Hydrogen production by the electrolysis of water is a green and efficient method, which is of great significance for achieving sustainable development. Molybdenum disulfide (MoS2) is a promising electrocatalyst for hydrogen evolution reaction (HER) due to its high electrochemical activity, low cost, and abundant reserves. In comparison to the noble metal Pt, MoS2 has poorer hydrogen evolution performance in water electrolysis. Therefore, further modifications of MoS2 need to be developed aiming at improving its catalytic performance. The present work summarizes the modification strategies that have been developed in the past three years on hydrogen evolution from water electrolysis by utilizing MoS2 as the electrocatalyst and following the two aspects of internal and external modifications. The former includes the strategies of interlayer spacing, sulfur vacancy, phase transition, and element doping, while the latter includes the heterostructure and conductive substrate. If the current gap in this paper’s focus on modification strategies for electrocatalytic hydrogen evolution in water electrolysis is addressed, MoS2 will perform best in acidic or alkaline media. In addition to that, the present work also discusses the challenges and future development directions of MoS2 catalysts.

The present work theoretically investigated propane oxidation dehydrogenation by utilizing N2O as an oxidant (N2O-ODHP) over Cu-BEA with three different types of active site, including monomeric Cu ([Cu]+), dimeric Cu ([Cu−Cu]2+), and distant monomeric Cu sites ([Cu]+—[Cu]+). Energetically, we calculated that the monomeric [Cu]+ is favorable for the αH dehydrogenation step (∆E = 0.05 eV), which, however, suffers from high barriers of N2O dissociation and βH dehydrogenation steps of 1.40 and 1.94 eV, respectively. Although the dimeric [Cu−Cu]2+ site with a Cu—Cu distance of 4.91 Å is much more favorable for N2O dissociation (0.95 eV), it still needs to overcome an extremely high barrier (∆E = 2.15 eV) for βH dehydrogenation. Interestingly, the distant [Cu]+—[Cu]+ site with the Cu—Cu distance of 5.82 Å exhibits low energy barriers for N2O dissociation (0.89 eV) and ODHP steps (0.01 and 0.33 eV) due to the synergistic effect of distant [Cu]+. The microkinetic analyses quantitatively verified the superior activity of the distant [Cu]+—[Cu]+ site with a reaction rate being eight to nine orders of magnitude higher than those of the monomeric and the dimeric Cu sites, and this is related to its ready charge-transfer ability, as shown by the partial Density of State (PDOS) analysis and the static charge differential density analysis in this study. Generally, the present work proposes that the distance between the [Cu]+ sites plays a significant and important role in N2O-ODHP over the Cu-based zeolite catalyst and modulates Cu—Cu distance, and this constitutes a promising strategy for highly-efficient Cu-zeolite catalyst design for N2O-ODHP.

Direct oxidation of methane to methanol (DMTM), constituting a major challenge for C1 chemistry, has aroused significant interest. The present work reports the synergistic effect of neighboring [Fe]--[Cu] cations, which can significantly boost the CH3OH productivity (100.9 and 41.9 → 259.1 μmol∙g−1cat∙h−1) and selectivity (0.28 and 17.6% → 71.7%) of the best performing Fe0.6%Cu0.68%-BEA (relative to monomeric Fe1.28%- and Cu1.28%-BEA) during the continuous H2O-mediated N2O DMTM. The combined experimental (in situ FTIR, D2O isotopic tracer technique) and theoretical (DFT, ab initio molecular dynamics (AIMD)) studies reveal deeper mechanistic insights that the synergistic effect of [Fe]--[Cu] can not only significantly favor active O production (ΔG = 0.18 eV), but also efficiently motivate the reaction following a H2O proton-transfer route (ΔG = 0.07 eV), eventually strikingly promoting CH3OH productivity/selectivity. Generally, the proposed strategy by employing the synergistic effect of bimetallic cations to modify DMTM activity would substantially favor other highly efficient catalyst designs.

A series of low HgCl2-supported catalysts (K-TX-O, K-WG-O, K-S20-O, K-S40-O, K-Fe0.8-O, K-Fe0.8-M, D-Fe0.8-M) was prepared and investigated for C2H2 catalytic abatement during highly purified HCl (HP-HCl) production process. The samples of D-Fe0.8-M, K-Fe0.8-M, and K-Fe0.8-O were found to exhibit much higher activities and better thermal stabilities than those of other samples. The characterization results of XRD, N2 adsorption/desorption, SEM, back scattered electron (BSE) and thermogravimetry (TG) revealed that: (i) the larger mesoporous volumes constituted one of the key factors leading to superior catalytic performances of D-Fe0.8-M, K-Fe0.8-M, and K-Fe0.8-O, which greatly facilitated better dispersions of the loaded HgCl2 species in comparison to other samples; (ii) the KCl additive could further improve the dispersions and thermal stabilities of the loaded the HgCl2 species due to the strong interactions between KCl and HgCl2 species, resulting in relatively higher catalytic behaviors of D-Fe0.8-M and K-Fe0.8-M than that of K-Fe0.8-O; (iii) the KCl/HgCl2 step-by-step loading strategy, wherein the KCl was initially loaded on the Fe0.8-AC substrate thereafter followed by HgCl2 loading, could further improve the catalytic behavior for D-Fe0.8-M due to additional improvements of HgCl2 dispersions. The deactivation and reactivation of D-Fe0.8-M during HP-HCl were also investigated, which suggested that partial deactivated D-Fe0.8-M by C2H3Cl accumulation could be efficiently reactivated by HCl treatment at T = 220 °C.