In this work, we have developed a mild, metal-free solution polycondensation protocol mediated by EDC and DMAP that enables the synthesis of bio-based polyesters from thermally labile monomers while overcoming key limitations of high-temperature melt polycondensation. We have prepared FDCA- and succinic acid-based homopolyesters, revealing distinct structure-property relationships between rigid furanic and flexible aliphatic systems. In addition, this methodology was extended to heteropolyesters via one-pot and sequential strategies, enabling compositional control. Structure-property relationships reveal that FDCA-based furanic polyesters exhibit higher Tg values and predominantly amorphous character, whereas succinic-acid-based analogs show higher Tonset values and selective crystallinity. This library of polymers establishes EDC/DMAP-mediated polycondensation as a versatile platform for sustainable materials design beyond the limits of conventional melt processing.

Chemoselective reduction of stable carboxylic acids to reactive aldehydes is of interest across many industries. While carboxylic acid reductases (CARs) are promising biocatalysts for this chemistry, poor chemoselectivity and low yield are commonly obtained when using less expensive crude lysate preparations and prerequisite ATP and NADPH regeneration systems. Here, we developed a highly chemoselective multienzyme cascade featuring a CAR and an ω-transaminase (TA) in crude lysate format, with conversion of the dicarboxylic acid terephthalic acid (TPA) into the diamine para-xylylenediamine (pXDA) as the model chemistry. We improved chemoselectivity for pXDA using engineered aldehyde-stabilizing Escherichia coli strains, though desired product yields remained modest. We next found that CAR activity was limited at high substrate loadings and overcame this bottleneck by modulating the ratio of polyphosphate (polyP6) to Mg2+, enabling volumetric scaling and increased substrate loading up to 50 mM TPA. We then showcased the portability of this platform across substrates, resulting in the synthesis of four other high-value amines from carboxylate precursors. The combination of high carboxyl group turnover, up to 93.5 mM under the tested conditions, and the simplicity of crude enzyme preparation is a promising platform for sustainable functional group interconversion.

Pyrolysis is a relatively mature process for recycling plastic waste, yet predictive kinetic models remain elusive due to the enormous number of radical reaction pathways, intermediates, and products. Starting from elementary hydrogen abstraction, random and chain-end β-scission reactions, we construct continuum population balance equations (PBEs) and discrete species balance equations (SBEs) to model polypropylene (PP) pyrolysis for realistic initial molecular weight distributions (MWDs) and reactor time and length scales. The framework accounts for the separate but coupled MWDs of alkanes, α-olefins, and α,ω-olefins polymers, along with the amounts of volatile alkanes and olefins generated during the reaction. We parameterized the model using rate constants from prior ab initio calculations. The model predicts the evolution of the polymer MWD, the degree of double-bond functionality, the number of scission events, and the amounts of volatile alkane and alkene products as a function of time. The predictions agree with experimental MWD data and resolve prior questions about the double-bond functionality (f) of volatile and nonvolatile products. We discuss how the model can help design processes to obtain products of the desired molecular weight and functionality.

This study presents a versatile, eco-friendly approach for synthesizing noble metal-free electrocatalysts by combining phytic acid (PA) with transition metals (M: Co, Mn, Ni, Cu). The resulting materials (MPA) feature metal phosphides or phosphates intricately embedded within an amorphous carbon matrix, with composition and structure highly dependent on the selected metal precursor. MnPA displayed notable oxygen reduction reaction (ORR) activity (EONSET = 0.85 V vs. RHE), while NiPA showed strong oxygen evolution reaction (OER) performance (EOER = 1.62 V vs. RHE), revealing the potential of phosphorus as a powerful dopant in carbon-based systems. This study highlights the tunability of electrocatalytic properties through metal selection and provides a sustainable pathway for designing high-performance ORR and OER electrodes. The results underscore the role of phosphorus chemistry in advancing next-generation energy conversion technologies.

Li-Mn-O materials are regarded as highly promising cathodes candidates for large-scale energy storage applications owing to the abundance, low cost, and low toxicity of manganese. Although existing reviews have explored certain Li-Mn-O cathode systems, such as LiMn2O4 and lithium-rich Mn-based oxides, a systematic analysis comprehensively correlating the structural characteristics, fundamental failure mechanisms, and corresponding modification strategies across different Li-Mn-O systems remains lacking. Few reviews have fully integrated multiscale failure mechanisms spanning from atomic-scale distortions to electrode-level performance degradation, along with synergistic mitigation strategies, which have yet to be systematically elucidated. Therefore, this review aims to bridge these research gaps by systematically integrating and critically evaluating recent groundbreaking advances in the mechanistic understanding and performance optimization of Li-Mn-O materials, covering the structural fundamentals, available synthesis methods, intrinsic mechanisms of structural instability and characterizations, and corresponding strategies for performance enhancement of Li-Mn-O materials. Furthermore, we propose perspectives on future research directions for high-stability Mn-based cathode materials, offering theoretical support for next-generation lithium battery technologies.

Developing highly efficient oxygen electrocatalysts to boost the kinetics of ORR and OER is essential to promoting the commercialization of Zn-air batteries. Co and Mn-based catalysts have been widely investigated in electrochemistry due to their variable valence states. Herein, Co-MnO-Mn3(PO4)2 synergetic composites (denoted CMO@NPC) are fabricated via phosphorylation pyrolysis of urea-treated Co-Mn-MOF as ORR and OER catalysts for the rechargeable ZAB. Due to differences in diffusion coefficients, Mn2+ is more readily transported to the surface, where it forms Mn3(PO4)2 outer framework to mitigate structural degradation during cycling. Moreover, the construction of Co-Mn heterojunctions can modulate the electron distribution, break the original electronic symmetry, and thereby optimize the adsorption strength of reaction intermediates. As a result, the optimal CMO@NPC-800 exhibits outstanding ORR and OER performance, delivering a potential difference of 0.701 V. DFT calculations reveal that the generation of a built-in electric field in the Co-MnO-Mn3(PO4)2 system, and the Co-Mn synergy optimizes the d-band center, thereby significantly reducing the reaction barriers for both ORR and OER. The aqueous ZAB based on the CMO@NPC-800 catalyst exhibits outstanding performance with a high peak power density (203.8 mW cm-2), a large specific capacity (793.5 mAh g-1), and long-term charge-discharge durability (1695 cycles).

FeOOH has emerged as a promising earth-abundant catalyst for water oxidation, with activity comparable to that of precious-metal oxides such as IrO2 and RuO2 under optimal conditions. Herein, we systematically investigate the effect of crystal structure on water oxidation activity using four FeOOH polymorphs (α, β, γ, and δ) under identical conditions. We demonstrate that the catalytic performance strongly depends on the crystal structure, with higher surface hydrophilicity leading to enhanced water oxidation activity. The same structure-dependent trend is observed under both electrochemical and photochemical conditions, indicating that the intrinsic catalytic properties of FeOOH govern the reaction irrespective of the reaction mode. Density functional theory calculations reveal that the adsorption energy for H2O on FeOOH surfaces correlates well with the experimentally observed activity, with δ-FeOOH exhibiting the highest performance. These findings identify interfacial hydrophilicity as a key descriptor for water oxidation on FeOOH polymorphs and provide design guidelines for the development of efficient, earth-abundant water oxidation catalysts.

The oxygen evolution reaction (OER) presents a significant kinetic bottleneck in photocatalytic water splitting and solar fuel production. To address this challenge, we designed and synthesized a donor-acceptor covalent organic framework (COF) with a cationic, electron-deficient pyrylium derivative monomer and an electron-rich 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde monomer to maximize potential donor-acceptor effect, extending the absorption and photon utilization to the red end of the visible region. Using a postsynthetic modification strategy, atomically dispersed Co2+ sites were precisely anchored onto the framework to construct Co-TTN-COF, a composite that integrates efficient light-harvesting and catalytic functions. Under visible-light irradiation, this catalyst demonstrates superior performance for water oxidation, achieving an average oxygen evolution rate of 249 μmol h-1 g-1. This work establishes a new strategy for the development of efficient and stable COF-based integrated photocatalytic systems.

With the development of the industry, traditional lithium-ion battery (LIB) technology is constantly improving, and new technologies are constantly breaking through, consolidating its dominant position in energy storage systems. However, the high manufacturing cost and inherent risks of organic electrolytes severely hinder the commercialization of LIBs. Therefore, developing low-cost and high-safety battery energy storage systems has become an urgent societal task. Research has shown that aqueous zinc-ion batteries (AZIBs) using high-safety and eco-friendly aqueous electrolytes effectively reduce the risk. In this work, a facile one-step hydrothermal approach was applied to prepare nanoflower-structured Na-NH4V4O10 cathode materials. This material exhibited a specific capacity of 619.22 mAh g[-1] at a current density of 0.1 A g[-1], along with a capacity of 128.84 mAh g[-1] when the current density rose to 5 A g[-1]. Meanwhile, a specific capacity of 245.63 mAh g[-1] was still retained even after 800 cycles at 1 A g[-1]. This research provides valuable insights into the fabrication of cathode materials targeted at AZIBs in subsequent studies.

The electrocatalytic nitrate reduction reaction (NtRR) offers a sustainable and promising alternative to the energy-intensive Haber-Bosch process for ambient ammonia (NH3) synthesis. However, its practical application is limited by sluggish reaction kinetics and low selectivity due to competing side reactions. Herein, we demonstrate the in situ transformation of cobalt oxyhydroxide (CoOOH) nanosheets into a well-defined quantum dot (QD) architecture induced by a graphdiyne (CoOOH@GDY). Experiments combined with theoretical results demonstrate that the noninteger charge transfer between sp-C and Co atoms at the interface enables precise electronic modulation, the formation of abundant low-coordination sites and grain boundaries, optimized adsorption ability for reaction intermediates, and high intrinsic catalytic activity. As a result, the obtained CoOOH@GDY electrocatalyst exhibited exceptional NtRR performance, achieving a remarkable Faradaic efficiency of 98.01%, a high NH3 yield rate of 1644 µmol h-1 cm-2 in 1 M KOH with 0.1 M NO3 -, and high operational stability. This work highlights the great potential of GDY-mediated interface engineering for the rational design of high-performance electrocatalysts.

The development of highly efficient and stable photocatalysts for the direct conversion of solar energy into chemical energy stands out as a critical frontier in mitigating global energy and environmental crises. Owing to their exceptional photoelectric properties, halide perovskites have emerged as highly promising candidates for photocatalysis. Here, we systematically review the structure, properties, and synthesis methods of halide perovskites, and summarize recent advances in their photocatalytic and photoelectrocatalytic applications. Specifically, we focus on photocatalytic hydrogen production, carbon dioxide reduction, organic pollutant degradation, and photoelectrochemical systems. Notably, key challenges continue to hinder their practical application, particularly inherent instability in aqueous environments, lead toxicity, and charge recombination losses. To this end, we critically evaluate emerging strategies designed to circumvent these bottlenecks, including composition engineering, heterostructure construction, and protective encapsulation. Furthermore, we highlight lead-free alternatives and integrated systems that balance catalytic activity, operational stability, and environmental compatibility. Collectively, we outline future research directions to realize sustainable solar-to-chemical energy conversion through the rational design of next-generation halide perovskite photocatalysts.

Faced with global energy and environmental challenges, seawater electrolysis has emerged as a promising route for marine resource utilization. However, its efficiency is limited by impurities and slow reaction kinetics. Although noble metal catalysts show high activity, their high cost and insufficient durability drive the search for alternatives. Perovskite oxides (ABO3) have gained attention due to their tunable structures, excellent stability, and outstanding catalytic activity. This review systematically explores the roles of perovskite oxides in seawater electrolysis, focusing on their design and function at each electrode. At the cathode, they are tailored to catalyze the hydrogen evolution reaction (HER) by improving electron transfer and adsorption. At the anode, the ABO3 structure enables both oxygen evolution reaction (OER) and chlorine evolution reaction (CER). The selectivity between OER and CER depends on lattice oxygen stability and the metal's relative affinity for oxygen and chlorine. In addition, this review covers the compositional flexibility, synthesis methods, and electrocatalytic performance of perovskite oxides in seawater electrolysis. Furthermore, modification strategies aimed at enhancing the activity, selectivity, and durability of perovskite oxides in seawater electrolytes are also discussed. Finally, we present the current challenges and propose future research directions.

To achieve the global carbon neutrality target by approximately 2050, the development and deployment of carbon-negative technologies based on green chemical principles have become an urgent strategic priority. Among various CO2 valorization routes, catalytic CO2 hydrogenation to methanol (CH3OH, CHM) has attracted intensive interest, in which indium oxide (In2O3) stands out as a highly promising candidate due to its unique properties in stabilizing key reaction intermediates for CH3OH synthesis. However, the practical implementation of pristine In2O3 is severely hindered by insufficient catalytic activity. To address the bottlenecks, a variety of multidimensional modification strategies have been rationally designed and extensively explored to tune the characteristics of In2O3-based catalysts, which include modulating properties of In2O3, tailoring properties of metal promoters and regulating metal-In2O3 interactions. In this review, we commence with a systematic discussion of the reaction mechanisms governing CHM over In2O3-based catalysts, then provide an in-depth summary and critical evaluation of the modification strategies for the rational design of In2O3-based catalysts, and finally highlight the most challenging issues and possible solutions in this rapidly evolving field to guide the rational design of the next-generation of efficient In2O3-based catalytic systems for sustainable CHM and the advancement of the circular carbon economy.

The solution-based fabrication of perovskite solar cells (PSCs) typically relies on high-purity materials, the cost of which limits commercial scalability. Here, we report an efficient strategy for directly synthesizing FAPbI3-based perovskite microcrystals (MCs) from industrial-grade precursors using formic acid (HCOOH) as a multifunctional additive and antisolvent in a synergistic process combining inverse temperature crystallization (ITC) and antisolvent-assisted precipitation. In situ grazing-incidence wide-angle X-ray scattering (GIWAXS) analysis reveals that formate anions (HCOO[-]) coordinate with Pb[2+] to regulate crystallization, passivate structural defects, and promote the direct formation of α-FAPbI3. An optimal HCOOH concentration (40%-60% v/v) was identified, achieving a high microcrystalline yield of 92.83% and effectively suppressing the formation of δ-FAPbI3. However, concentrations exceeding this range (>80% v/v) disrupt the precursor stoichiometry, leading to PbI2 impurity segregation. Thin films fabricated using the optimized microcrystals exhibited improved morphological uniformity, enhanced crystallinity, reduced nonradiative recombination losses, and extended charge carrier lifetimes. As a result, inverted-structure PSCs based on these MCs achieve a champion power conversion efficiency of 25.24% (0.07 cm[2]). This work presents a cost-effective and scalable route for producing high-quality perovskite materials and provides mechanistic insights into the dual functionality of HCOOH, offering valuable guidance for the advancement of low-cost, high-performance perovskite photovoltaic technologies.

We report direct evidence of distinct cation-CO2 adduct formation in ionic liquids (ILs) based on aprotic N-heterocyclic anions (AHAs), using a custom-designed in situ NMR (iNMR) method under conditions verified to achieve equilibrium speciation. These complexes are in addition to the primary anion-CO2 carbamate product. [13]C and [31]P NMR spectra of three triethyloctylphosphonium ([P2228][+]) AHA ILs all reveal two distinct carboxylate species, resulting from regioselective CO2 addition at both α-carbons of the asymmetric cation. The product ratios vary with temperature, and DFT-predicted pKa values confirm subtle differences in α-proton acidity. In contrast, a symmetric tetrahexylphosphonium ([P6666][+]) analog forms only a single cation-CO2 adduct, highlighting that multiple-site reactivity arises from chemical differentiation of α-positions rather than asymmetry alone. Surprisingly, ammonium and guanidinium-based AHA ILs previously considered completely inert toward carboxylation also exhibit weak but reproducible cation-CO2 signals, detected only under undiluted, isotopically enriched conditions. These findings expand the mechanistic understanding of AHA IL-CO2 chemistry and demonstrate that cation structure, particularly asymmetry and proton acidity, critically governs reactivity. The results provide a framework for designing ILs with tunable CO2 activation profiles for selective capture and release.