Dry reforming of methane (DRM) is an attractive route to utilize CO2 as a chemical feedstock with which to convert CH4 into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH4, thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

Semi-hydrogenation of acetylene in excess ethylene is a key industrial process for ethylene purification. Supported Pd catalysts have attracted most attention due to their superior intrinsic activity but often suffer from low selectivity. Pd single-atom catalysts (SACs) are promising to significantly improve the selectivity, but the activity needs to be improved and the feasible preparation of Pd SACs remains a grand challenge. Here, we report a simple strategy to construct Pd1/TiO2 SACs by selectively encapsulating the co-existed small amount of Pd nanoclusters/nanoparticles based on their different strong metal-support interaction (SMSI) occurrence conditions. In addition, photo-thermo catalysis has been applied to this process where a much-improved catalytic activity was obtained. Detailed characterization combined with DFT calculation suggests that photo-induced electrons transferred from TiO2 to the adjacent Pd atoms facilitate the activation of acetylene. This work offers an opportunity to develop highly stable Pd SACs for efficient catalytic semi-hydrogenation process.

The conversion of CH4 and CO2 to syngas using low-cost nickel catalysts has attracted considerable interest in the clean energy and environment field. Nickel nanoparticles catalysts suffer from serious deactivation due mainly to carbon deposition. Here, we report a facile synthesis of Ni single-atom and nanoparticle catalysts dispersed on hydroxyapatite (HAP) support using the strong electrostatic adsorption (SEA) method. Ni single-atom catalysts exhibit excellent resistance to carbon deposition and high atom efficiency with the highest reaction rate of 1186.2 and 816.5 mol.gNi−1.h−1 for CO2 and CH4, respectively. Although Ni single-atom catalysts aggregate quickly to large particles, the polyvinylpyrrolidone (PVP)-assisted synthesis exhibited a significant improvement of Ni single-atom stability. Characterizations of spent catalysts revealed that carbon deposition is more favorable over nickel nanoparticles. Interestingly, it was found that, separately, CH4 decomposition on nickel nanoparticle catalysts and subsequent gasification of deposit carbon with CO2 resulted in CO generation, which indicates that carbon is reacting as an intermediate species during reaction. Accordingly, the approach used in this work for the design and control of Ni single-atom and nanoparticles-based catalysts, for dry reforming of methane (DRM), paves the way towards the development of stable noble metals-free catalysts.

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