The electrocatalytic reduction of CO 2 (CO 2 ER) to liquid fuels is important for solving fossil fuel depletion. However, insufficient insight into the reaction mechanisms renders a lack of effective regulation of liquid product selectivity. Here, in situ surface-enhanced Raman spectroscopy (SERS) empowered by 13 C/ 12 C isotope exchange is applied to probing the CO 2 ER process on nanoporous silver (np-Ag). Direct spectroscopic evidence of the preliminary intermediates, *COOH and *OCO − , indicates that CO 2 is coordinated to the catalyst via diverse adsorption modes. Further, the relative Raman intensities of the above intermediates vary notably on np-Ag modified by Cu or Pd, and the liquid product selectivity also changes accordingly. Combined with density functional theory calculations, this study demonstrates that the CO 2 adsorption configuration is a critical factor governing the reaction selectivity. Meanwhile, *COOH and *OCO − are key targets in the initial stage regulating liquid product selectivity, which could facilitate future selective catalyst design.
Adsorbed atomic H (H*) facilitates indirect pathways playing a major role in the electrochemical removal of various priority pollutants. It is crucial to identify the atomic sites responsible for the provision of H*. Herein, through a systematic study of the distribution of H* on Pd nanocatalysts with different sizes and, more importantly, deliberately controlled relative abundance of surface defects, we uncovered the central role of defects in the provision of H*. Specifically, the H* generated on Pd in an electrochemical process increased markedly upon introducing defect sites by changing the morphology to ultrathin polycrystalline Pd nanowires (NWs), while dramatically reducing upon decreasing the number of surface defects through an annealing treatment. Benefiting from a proportion of H* up to 40% of the total H* species, the Pd NWs showed an electrochemical active surface area normalized rate constant of 13.8 ± 0.8 h m, which is 8-9 times higher than its Pd/C counterparts. The pivotal role of defect sites for the generation of H* was further verified by blocking such sites with Rh and Pt atoms, while theoretical calculation also confirms that the adsorption energy of H* on these sites is much higher than that on the Pd{111} facet.
AuPd bimetallic nanocatalysts exhibit superior catalytic performance in the cleavage of carbon-halogen bonds (C-X) in the hazardous halogenated pollutants. A better understanding of how Au atoms promote the reactivity of Pd sites rather than vaguely interpreting as bimetallic effect and determining which type of Pd sites are necessary for these reactions are crucial factors for the design of atomically precise nanocatalysts that make full use of both the Pd and Au atoms. Herein, we systematically manipulated the coordination number of Pd-Pd, d-orbital occupation state, and the Au-Pd interface of the Pd reactive centers and studied the structure-activity relationship of Au-Pd in the catalyzed cleavage of C-X bonds. It is revealed that Au enhanced the activity of Pd atoms primarily by increasing the occupation state of Pd d-orbitals. Meanwhile, among the Pd sites formed on the Au surface, five to seven contiguous Pd atoms, three or four adjacent Pd atoms, and isolated Pd atoms were found to be the most active in the cleavage of C-Cl, C-Br, and C-I bonds, respectively. Besides, neighboring Au atoms directly contribute to the weakening of the C-Br/C-I bond. This work provides new insight into the rational design of bimetallic metal catalysts with specific catalytic properties.
Respective detection of microplastics
(MPs) and nanoplastics (NPs)
is of great importance for their different environmental behaviors
and toxicities. Using spherical polystyrene (PS) and poly(methyl methacrylate)
(PMMA) plastics as models, the efficiency for sequential isolation
of MPs and NPs by membrane filtration and cloud-point extraction was
evaluated. After filtering through a glass membrane (1 μm pore
size), over 90.7% of MPs were trapped on the membrane, whereas above
93.0% of NPs remained in the filtrate. The collected MPs together
with the glass membrane were frozen in liquid nitrogen, ground, and
suspended in water (1 mL) and subjected to pyrolysis-gas chromatography-mass
spectrometry (Py-GC/MS) determination. The NPs in the filtrate were
concentrated by cloud-point extraction, heated at 190 °C to degrade
the extractant, and then determined by Py-GC/MS. For MPs and NPs spiked
in pure water, the method detection limits are in the range of 0.05–1.9
μg/L. The proposed method is applied to analyze four real water
samples, with the detection of 1.6–7.6 μg/L PS MPs and
0.6 μg/L PMMA MPs in three samples, and spiked recoveries of
75.0–102% for MPs and 67.8–87.2% for NPs. Our method
offers a novel sample pretreatment approach for the respective determination
of MPs and NPs.
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