Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liquid interfaces with a purpose of establishing correlations of size- and shape-dependent chemical and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a molecular level.

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Catalytic transformation of CH4 under a mild condition is significant for efficient utilization of shale gas under the circumstance of switching raw materials of chemical industries to shale gas. Here, we report the transformation of CH4 to acetic acid and methanol through coupling of CH4, CO and O2 on single-site Rh1O5 anchored in microporous aluminosilicates in solution at ≤150 °C. The activity of these singly dispersed precious metal sites for production of organic oxygenates can reach about 0.10 acetic acid molecules on a Rh1O5 site per second at 150 °C with a selectivity of ~70% for production of acetic acid. It is higher than the activity of free Rh cations by >1000 times. Computational studies suggest that the first C–H bond of CH4 is activated by Rh1O5 anchored on the wall of micropores of ZSM-5; the formed CH3 then couples with CO and OH, to produce acetic acid over a low activation barrier.

The majority of harmful atmospheric CO and NO x emissions are from vehicle exhausts.A lthough there has been success addressing NO x emissions at temperatures above 250 8 8Cw ith selective catalytic reduction technology,e missions during vehicle cold start (when the temperature is below 150 8 8C), are am ajor challenge.H erein, we showw ec an completely eliminate both CO and NO x emissions simultaneously under realistic exhaust flow, using ah ighly loaded (2 wt %) atomically dispersed palladium in the extra-framework positions of the small-pore chabazite material as aC O and passive NO x adsorber.U ntil now,a tomically dispersed highly loaded (> 0.3 wt %) transition-metal/SSZ-13 materials have not been known. We devised ag eneral, simple,a nd scalable route to prepare such materials for Pt II and Pd II . Through spectroscopyand materials testing we showthat both CO and NO x can be simultaneously completely abated with 100 %e fficiency by the formation of mixed carbonyl-nitrosyl palladium complex in chabazite micropore.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Pervaporation has been regarded as a promising separation technology in separating azeotropic mixtures, solutions with similar boiling points, thermally sensitive compounds, organic-organic mixtures as well as in removing dilute organics from aqueous solutions. As the pervaporation membrane is one of the crucial factors in determining the overall efficiency of the separation process, this article reviews the research and development (R&D) of polymeric pervaporation membranes from the perspective of membrane fabrication procedures and materials.

Heterogeneous catalysis performs on specific sites of a catalyst surface even if specific sites of many catalysts during catalysis could not be identified readily. Design of a catalyst by managing catalytic sites on an atomic scale is significant for tuning catalytic performance and offering high activity and selectivity at a relatively low temperature. Here, we report a synergy effect of two sets of single-atom sites (Ni1 and Ru1) anchored on the surface of a CeO2 nanorod, Ce0.95Ni0.025Ru0.025O2. The surface of this catalyst, Ce0.95Ni0.025Ru0.025O2, consists of two sets of single-atom sites which are highly active for reforming CH4 using CO2 with a turnover rate of producing 73.6 H2 molecules on each site per second at 560 °C. Selectivity for producing H2 at this temperature is 98.5%. The single-atom sites Ni1 and Ru1 anchored on the CeO2 surface of Ce0.95Ni0.025Ru0.025O2 remain singly dispersed and in a cationic state during catalysis up to 600 °C. The two sets of single-atom sites play a synergistic role, evidenced by lower apparent activation barrier and higher turnover rate for production of H2 and CO on Ce0.95Ni0.025Ru0.025O2 in contrast to Ce0.95Ni0.05O2 with only Ni1 single-atom sites and Ce0.95Ru0.05O2 with only Ru1 single-atom sites. Computational studies suggest a molecular mechanism for the observed synergy effects, which originate at (1) the different roles of Ni1 and Ru1 sites in terms of activations of CH4 to form CO on a Ni1 site and dissociation of CO2 to CO on a Ru1 site, respectively and (2) the sequential role in terms of first forming H atoms through activation of CH4 on a Ni1 site and then coupling of H atoms to form H2 on a Ru1 site. These synergistic effects of the two sets of single-atom sites on the same surface demonstrated a new method for designing a catalyst with high activity and selectivity at a relatively low temperature.

Cu-based catalysts have attracted much interest in CO 2 hydrogenation to methanol because of their high activity. However, the effect of interface, coordination structure, particle size and other underlying factors existed in heterogeneous catalysts render to complex active sites on its surface, therefore it is di cult to study the real active sites for methanol synthesis. Here, we report a novel Cu-based catalyst with isolated Cu active sites (Cu 1 -O 3 units) for highly selective hydrogenating CO 2 to methanol at low temperature (100% selectivity for methanol at 180 o C). Experimental and theoretical results reveal that the single-atom Cu-Zr catalyst with Cu 1 -O 3 units is only contributed to synthesize methanol at 180 o C, but the Cu clusters or nanoparticles with Cu-Cu or Cu-O-Cu active sites will promote the process of reverse water gas shift (RWGS) side reaction to form undesirable byproducts CO. Furthermore, the Cu 1 -O 3 units with tetrahedral structure could gradually migrate to the catalyst surface for accelerating CO 2 hydrogenation reaction during catalytic process. The high activity isolated Cu-based catalyst with legible structure will be helpful to understand the real active sites of Cu-based catalysts for methanol synthesis from CO 2 hydrogenation, thereby guiding further design the Cu catalyst with high performance to meet the industrial demand, at the same time as extending the horizontal of single atom catalyst for application in the thermal catalytic process of CO 2 hydrogenation.

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