Zhihao Yu

Nitrogen‐containing chemicals are indispensable to modern society, among which lactams occupy a central position owing to their extensive use as polymer precursors, high‐performance solvents, and pharmaceutical building blocks. Conventional petroleum‐based production routes, however, are increasingly constrained by environmental and resource concerns, underscoring the urgency of developing sustainable alternatives from renewable biomass. Despite growing research activity, existing reviews on biomass‐derived lactam synthesis remain fragmented, typically concentrating on a limited number of established pathways and lacking a systematic mapping of renewable feedstocks, reaction networks, and catalytic strategies. To bridge these gaps, this review provides a systematic overview of representative biomass‐based lactams, with emphasis on γ‐, δ‐, and ε‐lactams, by correlating diverse renewable feedstocks with their corresponding synthetic routes under heterogeneous catalysis. This work aims to establish a coherent framework for biomass valorization and to offer conceptual and practical guidance for advancing efficient, selective, and sustainable lactam synthesis.

Gamma‐Valerolactone (GVL) has emerged as a promising biomass‐derived solvent for the catalytic conversion of sugars into furan chemicals such as 5‐hydroxymethylfurfural and furfural. Although GVL‐based solvent systems have demonstrated superior performance, the mechanistic roles of GVL are often described qualitatively and remain insufficiently clarified. This review systematically synthesizes recent advances and organizes insights from the literature to elucidate the roles of GVL in sugar‐to‐furan conversion. The effects of GVL‐based solvents are summarized into several interconnected aspects, including enhanced substrate solubility, regulation of reaction pathway selectivity, stabilization of key transition states, mediation of reactant enrichment, and facilitation of product separation. These insights highlight GVL as a multifunctional reaction medium rather than an inert solvent and provide guidance for the rational design of solvent systems for efficient biomass valorization.

A template-assisted approach was employed to synthesize a MOF-on-MOF derived catalyst for the selective oxidation of 5-hydroxymethylfurfural (5-HMF) to produce 2,5-furandicarboxylic acid (FDCA). Characterization revealed that the catalyst forms a cobalt–manganese metal oxide composite phase with a hierarchical porous structure and uniformly distributed Co/Mn active sites. The oxygen vacancies work together with the Lewis acid sites to gradually oxidize the hydroxyl and aldehyde groups in 5-HMF. In the context of reaction conditions that have been identified as optimal (140 °C, 6 h, 50 mg catalyst, 5.88 mol L⁻¹ H₂O₂), the yield of FDCA was 87.55%, accompanied by 5-HMF conversion rate of 98.66%. The catalyst exhibited exceptional cycling stability, sustaining an FDCA yield exceeding 75% across five cycles. Mechanism studies indicate that the Co–Mn bimetallic synergistic effect optimizes the reaction pathway through electron transfer and oxygen species activation, while the microporous structure prolongs the residence time of intermediates through confinement effect, promoting multi-step oxidation. Compared with the single-metal MOFs derived catalysts, this catalyst has significantly improved adsorption performance and oxidation efficiency, providing an efficient solution for the green synthesis of the bio-based polyester monomer FDCA.

Defect engineering combined with thermal activation enhances dual-origin Brønsted acidity in UiO-66, enabling superior fructose dehydration to HMF and offering a tunable strategy for efficient biomass conversion.

The safe and resource-efficient utilization of waste incineration fly ash (WIFA) has emerged as a pressing challenge in solid waste management. In this work, WIFA was used to prepare a bifunctional catalyst (Metals_x/4@WIFA-S) for the production of levulinic acid (LA) from glucose. The yield of LA was 42.3% with water as the solvent. Moreover, adding 20% γ-valerolactone (GVL) to the system increased the yield to 50.7%. Reaction kinetics and molecular dynamics simulations were applied to elucidate the mechanism by which the solvent system enhanced the catalytic performance of the Metals_x/4@WIFA-S catalyst. Additionally, the environmental risks of WIFA in the preparation of catalysts were evaluated. The dioxin decomposition rate in the catalyst was calculated to be 99.87%, effectively achieving the detoxification of the catalyst. The concentration of heavy metals in the hydrolysate complied with emission standards, thereby reducing environmental risk. This study confirms that waste incineration fly ash-based bifunctional catalysts are effective and safe catalysts with great potential for application in biomass catalysis.