Fuwei Li

Phosphine-containing porous organic polymers are candidate materials that could realize heterogenization of the homogeneous phosphine-metal catalysts. However, their succinct synthesis from the commercialized phosphines directly is still a challenge. This work pioneers a Brønsted acid-catalyzed molecular Lego assembly, enabling modular construction of fluorinated phosphine-containing polymers (FPPs) from commercial building blocks - aryl phosphines or their metal complexes - in one step. By simply introducing a third molecular-Lego module with rigid skeleton (e.g., spirobifluorene, triptycene), the porosity of FPPs can be precisely engineered while maintaining good to high yields (60%-98%), demonstrating the plug-and-play versatility of this strategy. This work presents the synthesis of 18 different structures of FPPs with distinct structures. Among them, the Ru complex-derived FPPs-10 shows excellent CO2 uptake capability (1.15 mmol·g-1 at 0 °C) and exhibits exceptional performance in N-formylation reaction: high activity (turnover number up to 1.41 × 105), and good stability (reused at least for 5 cycles), while maintaining broad alkylamine compatibility. Overall, this work establishes a molecular Lego-like assembly paradigm for the on-demand design and regulation of phosphine-based heterogeneous catalysts.

Regulating interfacial electronic structure of oxide-metal composite catalyst for the selective transformation of biomass or plastic waste into high-value chemicals through specific C–O bond scission is still challenging due to the presence of multiple reducible bonds and low catalytic activity. Herein, we find that the inverse catalyst of 4CeO_x/Ni can efficiently transform various lignocellulose derivatives and polyether into the corresponding value-added hydroxyl-containing chemicals with activity enhancement (up to 36.5-fold increase in rate) compared to the conventional metal/oxide supported catalyst. In situ experiments and theoretical calculations reveal the electron-rich interfacial Ce and Ni species are responsible for the selective adsorption of C–O bond and efficient generation of H^δ− species, respectively, which synergistic facilitate cleavage of C–O bond and subsequent hydrogenation. This work advances the fundamental understanding of interfacial electronic interaction over inverse catalyst and provides a promising catalyst design strategy for efficient transformation of C–O bond.

The carbon dioxide electroreduction reaction (CO₂RR) to carbon monoxide (CO) is a promising avenue to store renewable energy. Gold (Au) is a critical component of catalysts for CO production in the CO₂RR. Still, the high cost of Au together with the low mass activity hinders its potential towards practical CO₂RR application. Here we report a strategy of catalyst design, oxygen vacancy modulation via controlling Au/ceria interface structures, to promote Au mass activity for CO production (j_CO,mass) in the CO₂RR. Through ceria-nanocube-supported Au nanoparticle fabrication, we construct Au/CeO₂{100} interfaces with high concentration of oxygen vacancies facilitating CO₂ adsorption and activation. We achieve, at 200 mA cm⁻², a record j_CO,mass of 678 mA mg_Au ⁻¹ in the CO₂RR, a 1.3× improvement relative to the best prior reports.

Cu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation‐gel method and studied for the selective hydrogenation of syngas or biomass‐based diethyl malonate (DEM) to valuable 1,3‐propanediol (1,3‐PDO). The Ga‐promoted 70Cu6Ga/SiO₂ catalyst was found to exhibit the highest catalytic performance, achieving 100 % DEM conversion and 76.6 % 1,3‐PDO selectivity under reaction conditions of 160 °C and 8 MPa H₂. The 70Cu6Ga/SiO₂ bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO₂ catalyst in a continuous flow reactor over 180 h time‐on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu²⁺ species, and thus increased the proportion of Cu⁺ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu⁰ and Cu⁺ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO₂ bimetallic catalysts.

Solvent effects add a new dimension for tuning the activity and selectivity of heterogeneous catalytic reactions, which is extensively employed in the hydrogenation of unsaturated compounds with multiple functional groups. In this concept, we briefly summarize recent developments on how the solvent effects affect the catalytic performance from the following aspects: 1) the polarity of the solvent can influence the interaction between the solvent and the reactant or intermediate; 2) the composition of mixed solvent can influence the reactivity of the reactant or intermediate; 3) solvent effect varies with the metal identity and support; 4) the solvent can induce surface modification of the supported catalysts. This summarization will provide insights into the rational development of efficient and selective heterogeneous hydrogenation catalytic system to realize the precise synthesis of desired chemicals.

The development of effective and stable non‐precious catalysts for hydrogenation of ester to diols remains a challenge. Herein, the catalytic hydrogenation of ethyl lactate (EL) to 1,2‐propanediol (1,2‐PDO) with supported Co catalysts derived from layered double hydroxides (LDHs) is investigated. Catalytic tests reveal that LDH‐derived Co catalysts exhibit the best catalytic performance with 98 % of EL conversion and >99 % of 1,2‐PDO selectivity at mild conditions, compared with other Co catalysts (supported on Al₂O₃, and TiO₂) and LDH‐derived Cu catalysts. Due to the strong interaction among Co and Al matrix, the main composition is metallic Co⁰ and CoO after reduction at 600 °C. Besides, the catalyst shows good recyclability in the liquid phase hydrogenation. The superior catalytic performance can be attributed to the synergistic effect between Co⁰ and CoO, in which H₂ molecule is activated on Co⁰ and EL is strongly adsorbed on CoO via hydroxyl groups.

The CO₂ hydrogenation on Pt(111) proceeds with the increase of CO coverage and this can notably reduce the barrier of CH₄ and C₂H₅OH formation as compared with pristine Pt(111).

Ni‐based catalysts have been widely studied in the hydrogenation of CO₂ to CH₄, but selective and efficient synthesis of higher alcohols (C₂₊OH) from CO₂ hydrogenation over Ni‐based catalyst is still challenging due to successive hydrogenation of C1 intermediates leading to methanation. Herein, we report an unprecedented synthesis of C₂₊OH from CO₂ hydrogenation over K‐modified Ni−Zn bimetal catalyst with promising activity and selectivity. Systematic experiments (including XRD, in situ spectroscopic characterization) and computational studies reveal the in situ generation of an active K‐modified Ni−Zn carbide (K‐Ni₃Zn₁C_0.7) by carburization of Zn‐incorporated Ni⁰, which can significantly enhance CO₂ adsorption and the surface coverage of alkyl intermediates, and boost the C−C coupling to C₂₊OH rather than conventional CH₄. This work opens a new catalytic avenue toward CO₂ hydrogenation to C₂₊OH, and also provides an insightful example for the rational design of selective and efficient Ni‐based catalysts for CO₂ hydrogenation to multiple carbon products.