Guowu Zhan

Microbial electrosynthesis (MES) empowers one-step conversion of CO2 to long-chain chemicals under mild conditions, enabling sustainable biomanufacturing and achievement of a circular carbon economy. Although the construction of biohybrids has been explored to enhance the inherently low efficiency of MES, whether the binding modes between nanomaterials and microorganisms dictating CO2 conversion efficiency remain elusive. To address this query, we constructed biohybrids with three distinct integration modes (namely, internalization, outer membrane-contact, and transenvelope) between nanomaterials and Shewanella, enabling to proceed CO2-to-malate conversion. Upon MES-driven CO2-to-malate conversion, the transenvelope biohybrid constituted by polydopamine and Shewanella achieved a marked gram-scale malate titer of 19.14 mmol/L, as a result of the distinctive transenvelope capacity of polydopamine stretching from the extracellular to the intracellular membrane. This transenvelope capacity imparts extended electron transfer pathways spanning from the cytoplasmic membrane to the extracellular space, significantly reducing interfacial barriers at the electrode-microorganism interface and greatly promoting NADH and ATP synthesis for malate synthesis, which can enhance NADH synthesis. This work proposes the construction of a transenvelope biohybrid to optimize microbial metabolism, offering an alternative for the efficient valorization of CO2 to carbon-negative long-chain chemicals.

The integrated hydrodeoxygenation isomerization of fatty acids into iso-alkane fuels remains a significant challenge, as it requires simultaneously high deoxygenation activity and precise isomerization selectivity.

Catalytic hydrogenation of CO2 has been widely explored for producing chemicals and fuels, though its environmental and economic benefits remain context-dependent. Recently, In2O3-based catalysts have attracted significant interest because of their distinctive defect chemistry. These defect sites facilitate CO2 adsorption and activation and influence subsequent reaction pathways and product selectivity. This review highlights recent advances in In2O3-based catalytic systems for CO2 hydrogenation, emphasizing structure–activity relationships, modulation strategies, and underlying mechanisms. We begin by delineating the fundamental role of oxygen vacancies in CO2 adsorption and activation. Subsequently, we discuss various material design strategies, including defect engineering, interface regulation, and composite architecture construction, and analyze their impacts on catalytic performance. Furthermore, the product distribution is comprehensively examined, covering the formation pathways and selectivity control for C1 products (e.g., methanol), C2+ hydrocarbons (e.g., olefins and aromatics), and oxygenates. Emphasis is placed on product-oriented catalyst design and the evolution from intrinsic active-site regulation to multisite cooperation and reaction-pathway control. By linking catalyst architecture, complementary catalytic functions, intermediate evolution, and reaction pathways with product selectivity, we provide design principles for selective CO2 hydrogenation over In2O3-based catalysts.

Although Pd/ZrO2 represents a highly promising catalyst for CO2 hydrogenation, it still faces challenges such as low methanol selectivity and intense competing side reactions. In this study, we precisely constructed an In2O3 interfacial layer between Pd and ZrO2 by atomic layer deposition (denoted as Pd/xIn2O3/ZrO2, where x represents the number of atomic layer deposition cycles) and systematically investigated the role of this interlayer in modulating the catalyst microstructure, reaction pathways, and methanol selectivity. Catalytic performance evaluation results reveal that under reaction conditions of 320 °C and 3 MPa, the Pd/10In2O3/ZrO2 catalyst exhibits the best performance for CO2 hydrogenation to methanol, whereby the methanol selectivity was significantly enhanced from 6.6% to 76.6%, and the methanol space-time yield increased by approximately 6 times (2.40 vs. 13.37 gMeOH·gPd–1·h–1) when compared to pristine Pd/ZrO2 catalyst. Multifaceted characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrate that the introduction of In2O3 substantially strengthens CO2 adsorption and activation, promotes further hydrogenation of the key CO* intermediate, and establishes a dual-path synergistic mechanism involving both formate and CO-hydrogenation routes, thereby effectively suppressing the formation of the byproduct CO. Collectively, this work demonstrates that catalyst interface engineering via atomic layer deposition provides an effective strategy for tuning the reaction network and optimizing methanol selectivity in catalytic CO2 hydrogenation systems.

Biomass-plastic catalytic co-pyrolysis offers a promising route to aromatics, yet high-value monocyclic aromatic (MAH) selectivity remains challenged by the complex interdependencies of reaction parameters. Herein, we present a machine learning-guided strategy to maximize MAH production from the co-pyrolysis of rice straw and polypropylene. Central to this strategy is a hierarchical HZSM-5 zeolite synthesized using rice husk ash as the sole silica source. A hybrid methodology combining response surface methodology and machine learning models was employed to optimize four critical variables: temperature, feedstock mass ratio, catalyst Si/Al ratio, and catalyst loading. Under the optimal conditions, an exceptional MAH content of 71.7% was achieved. The biomass-derived catalyst exhibited superior activity and excellent stability. A cradle-to-gate assessment further revealed category-specific environmental differences between the rice-husk-derived and commercial zeolite production routes under the adopted inventory assumptions. This work establishes a data-driven platform for the efficient upcycling of waste into chemical feedstocks.

A sustainable one-pot hydrothermal strategy is reported for the synthesis of a core–shell Bio-Z5@NiFe catalyst utilizing rice husk derived biogenic silica. Ethylenediamine and EDTA-2Na function as chelating ligands to confine Ni and Fe species at the zeolite crystallization front, yielding a uniform, approximately 20 nm thick bimetallic coating intimately wrapped around the siliceous framework. This architectural precision circumvents the metal agglomeration endemic to conventional impregnation methods, while simultaneously providing a larger external surface area, enhanced metal dispersion, and intimate metal-acid proximity. In the hydrodeoxygenation of stearic acid, the optimized Bio-Z5@5Ni2Fe achieves complete conversion with exceptional selectivity exceeding 96% for n-octadecane under mild conditions. The catalyst exhibits remarkable substrate generality across C12–C18 fatty acids, consistently delivering >94% selectivity to linear alkanes, and retains >90% of its initial activity over four consecutive cycles. In situ DRIFTS and kinetic profiling elucidate a spatially concerted metal-acid relay mechanism. Spectroscopic evidence confirms that the bimetallic interface synergistically stabilizes bidentate and monodentate carboxylate intermediates, polarizing the C═O bond to facilitate hydrogen transfer. The proximity between the NiFe shell and Brønsted acid sites ensures the instantaneous rehydrogenation of transient α-olefin intermediates immediately following alcohol dehydration, thereby quenching decarbonylation and decarboxylation pathways. This work establishes a robust paradigm converging biomass valorization with atomic-level control over adsorption geometry and reaction trajectories for advanced biofuel production.

Thin-film nanocomposite (TFN) membranes show great potential for molecular separations, yet their fabrication typically involves multiple steps, including separate nanofiller synthesis, followed by interfacial polymerization. In this work, we report a one-step strategy to fabricate TFN membranes by synchronizing interfacial coordination and polymerization at an ionic liquid/water interface, directly forming an FeTCPP/polyamide hybrid layer on a poly(m-phenyleneisophthalamide) substrate. The membrane prepared with ethanol as a cosolvent in the aqueous phase (denoted TFN-E) was compared with its ethanol-free counterpart (TFN) and a conventional thin-film composite (TFC) membrane in terms of morphology, microstructure, physicochemical properties, and organic solvent nanofiltration (OSN) performance. The effects of nanomaterial loading and ethanol-to-water ratio were investigated. The reaction pathways and the role of ethanol were elucidated. The optimized TFN-E membrane exhibited a permeance 16 times as high as that of the nanomaterial-free TFC membrane (2.4 vs. 0.15 L m–2 h–1 bar–1) while maintaining a high rejection of Congo Red/ethanol. It also demonstrated excellent stability and durability in a variety of organic solvents. This work presents a novel and efficient one-step fabrication route for high-performance TFN membranes for the OSN applications.

The direct hydrogenation of CO2 to light aromatics (BTX) suffers from poor product selectivity owing to uncontrolled intermediate evolution and divergent reaction pathways. Herein, we report a rationally designed trifunctional GaZnZrOx/SAPO-34/ZSM-5 catalyst that enables highly efficient CO2-to-aromatics conversion via an integrated relay strategy. The system operates through a spatially organized relay process: CO2 is hydrogenated to methanol over GaZnZrOx, subsequently undergoing cascade C−C coupling and aromatization reactions within a hierarchically structured dual-zeolite domain. The pivotal innovation lies in the kinetic molecular-sieving function of SAPO-34, which discriminatively regulates intermediate diffusion. It preferentially facilitates ethylene transport (diffusion coefficient: 19.0 Å2/ps) to the adjacent ZSM-5 while selectively retarding heavier olefins, thereby effectively channeling the key intermediate toward BTX aromatization. The optimized catalyst exhibits 25.0% CO2 conversion with 81.8% aromatic selectivity under 360 °C and 30 bar. Notably, the BTX space-time yield reaches 78.4 mgproduct·gcat.−1·h−1, accounting for 49.5% of total aromatics and substantially exceeding the performance of single-zeolite counterparts. In situ spectroscopic studies further identify a sustained cracking-aromatization cycle that upgrades polycyclic and heavy intermediates into lighter BTX. This work elucidates the decisive role of precision molecular diffusion management in hierarchical zeolite catalysis, establishing a catalyst design principle for the selective conversion of CO2 to valuable aromatics.