Doping heteroatoms into the Cu/ZnO/Al2O3 catalyst is an effective strategy to enhance its performance in selective CO2 hydrogenation to methanol. However, a systematic understanding of how different dopants influence CO2 adsorption and the reaction energy landscape remains elusive. Herein, we combine theoretical calculations and experimental validation to address this gap. Density functional theory (DFT) calculations were first performed to screen a series of dopants, including Zr, Mg, Co, Y, Au, Ga, Pd, and Ca. Among them, Zr, Mg, and Co exhibited promising theoretical predictions and were subsequently synthesized and tested experimentally. Both theoretical and experimental results confirmed Zr as the most effective dopant, affording optimal CO2 adsorption energy and the lowest energy barrier for the rate-determining step (formate hydrogenation to H2COO*). Comprehensive characterization reveals that Zr doping induces stronger electron transfer from ZnO to Cu, thereby enhancing the electronic metal-support interaction (EMSI). The strengthened EMSI renders the Cu species more electron-rich, which promotes CO2 adsorption, facilitates the formation of key intermediates (e.g., formate and methoxy), improves the dispersion of Cu nanoparticles, and boosts H2 spillover. Under industrially relevant conditions (280 ℃, 5 MPa), the Zr-modified Cu/ZnO/Al2O3 catalyst achieves a high space‑time yield of 566.65 gMeOH∙kgcat-1∙h−1 and a CO2 conversion rate of 22.54%. Our findings highlight that modulating EMSI is a promising design strategy for CO2 hydrogenation catalysts.

To overcome the limited tolerance of microalgal strains to high CO2 levels and the non-directional nature of traditional physicochemical mutagenesis, long-term multi-cycle acclimation under 10%-100% CO2 was employed to domesticate Nannochloropsis oceanica with the aim of elucidating its temporal transcriptional regulation and genetic adaptation strategies. Under multi-cycle acclimation at 55% CO2, chloroplast-associated genes underwent mutations that promoted accelerated chloroplast development, enhanced photosystem II efficiency, enhanced Calvin cycle activity, and reduced photodamage. The temporal sequence of adaptive gene regulation was characterized by (1) reduced respiratory energy expenditure, (2) accelerated chloroplast biogenesis, (3) enhancement of photoreaction, (4) increased dark reaction rates, and (5) stimulation of cell proliferation, ultimately promoting biomass accumulation. In contrast, acclimation under 100% CO2 resulted in increased DNA damage and the accumulation of harmful mutations. Key functions, including photosystem II stability factor, nucleotide excision, and mismatch repair, were impaired. This disruption of genetic stability and transcriptional regulation resulted in reduced biomass growth and carbon fixation. Compared to the wild-type strain, the 55% CO2-domesticated microalgae exhibited a 78% increase in biomass dry weight and a 3-fold increase in carbon fixation under a 95% CO2 environment. Expression levels of PSII core proteins, carbon fixation rate-limiting enzymes, and cyclin genes were significantly upregulated. These findings demonstrate that long-term 55% CO2 domestication promoted the enrichment of beneficial mutations in photosynthetic carbon fixation and cell division genes, conferring stable tolerance to high CO2. This cost-effective and simple strategy provides a viable approach for developing microalgal strains suitable for industrial flue-gas CO2 mitigation.

To strengthen deoxygenation and bond-breaking ability of fatty acid methyl esters in microalgae oil for bio-jet fuel production, Co and Mo ions were co-doped into the Ni-based metal-organic framework (Ni-BDC-NH2) by ion-exchange method for the first time, and trimetallic Co-Mo-Ni catalysts was synthesized after pyrolysis. Co-doping of Co and Mo ions provided more active metal sites and enhanced electron transfer (Co -> Ni -> Mo). Due to the electronegativity order of Co < Ni

To improve the durable water-resistance of a metal-organic framework for atmospheric CO2 adsorption, hydrophobic oleylamine was employed to modify KAUST-7 by applying a protective layer of aliphatic hydrocarbons. Density functional theory (DFT) calculations revealed the delocalization of the p orbital of nitrogen in OLA and the d orbital of nickel in KAUST-7, indicating overlapping energy levels and the formation of coordination chemical bonds. At the-4.3 eV resonance peak, the overlap integral accounts for 78.6% of the N 2p states, confirming the formation of bonds. At-3.0 eV, the overlap reaches 92%, involving multiple Ni 3d sub-orbitals. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the formation of N-Ni bonds upon loading oleylamine on KAUST-7, leading to an increase in C=C bonds and C-C bonds. X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis confirmed the successful deposition of oleylamine on KAUST-7 in the optimal ratio while maintaining its crystallinity. The incorporation of 9 wt% OLA@KAUST-7 preserved the porous structure, enhancing the atmospheric CO2 adsorption capacity from 1.22 to 1.33 mmol/g. The contact angle of KAUST-7 loaded with 33 wt% oleylamine increased from 26.36 degrees to 103.7 degrees, significantly improving its hydrophobic properties. Breakthrough curves demonstrated a significant increase in the breakthrough time of KAUST-7 with oleylamine(OLA) loading, indicating a substantial improvement in CO2 adsorption capacity at an air relative humidity of 40%. The OLA@KAUST-7 composite material was directly introduced into the liquid culture medium as a carbon transport carrier, increasing the biomass of chlorella by 114%. Notably, the crystallinity of OLA@KAUST-7 remained intact even after 31 days of water immersion.

To reutilize corrosion inhibitor wastewater in various industries for microalgae cultivation, the toxic effects of benzotriazole (BTA), a common and refractory pollutant, on photosynthesis and metabolic pathways of Chlorella pyrenoidosa (C. pyrenoidosa) were first investigated. When the BTA concentration increased from 0 to 400 mg/L, C. pyrenoidosa cells became more wrinkled and broken. This structural damage led to an increase in cell fractal dimensions, a higher ratio of cell fragments, and elevated levels of humic-like substances in soluble extracellular polymeric substances. Due to the toxicity of BTA, both superoxide dismutase (SOD) activity and malondialdehyde (MDA) content increased substantially, indicating severe lipid peroxidation. To elucidate the underlying mechanisms, proteomic analysis was employed, revealing that BTA significantly downregulated key components like the D1 protein and photosynthetic antenna pathways. Consequently, when exposed to higher BTA concentrations (≥300 mg/L), the chlorophyll fluorescence parameters and photosynthetic oxygen release rates markedly decreased. Furthermore, the synthesis of pigments was severely inhibited at these concentrations, resulting in a drastic reduction in overall microalgal biomass production. Instead, upregulated DNA replication and sulfur assimilation indicated the activation of cellular tolerance mechanisms under moderate stress. However, exposure to 100 mg/L BTA exhibited lower toxicity toward chlorophyll fluorescence and photosynthetic pigment synthesis, leading to a marginal decrease in biomass production rather than severe inhibition. Therefore, wastewater containing low concentrations of BTA can be effectively utilized for practical microalgae cultivation.

Highlights➢ Transient multiphysics simulation of CO2 to methanol MEA electrolyzers.➢ Voltage loading strategies and catalyst layer structure optimize methanol yield and energy consumption.

The electroreduction of CO2 to methanol offers a promising route for carbon utilization and green fuel synthesis. However, this multi-step transformation requires that catalysts enable both efficient CO2 activation and deep conversion of *CO intermediate, which is a synergy difficult to achieve with a molecular catalyst such as cobalt phthalocyanine. Herein, a metallic-molecular dual-site catalyst featuring nanoscale colocalization of Ag clusters and nitro-substituted cobalt phthalocyanine (nCoPc) on carbon nanotubes (nCoPc/Ag@CNT) is constructed. Experimental and DFT analyses reveal that nCoPc is dispersed on amorphous Ag nanoparticles to form tightly coupled heterointerfaces via Ag-O linkages, which induces pronounced charge redistribution. This heterointerfacial effect promotes *CO spillover from the Ag site to the adjacent Co site and distorts the Co-N4 configuration, which moderates *CO adsorption and lowers the *CO-to-*CHO energy barrier by 0.10 eV to facilitate *CO activation. Consequently, nCoPc/Ag@CNT achieves a Faradaic efficiency (FECH3OH) of 72.7% in an H-type cell and a high partial current density (jCH3OH) of 98.3 mA & sdot;cm- 2 in a flow cell, markedly outperforming physically mixed nCoPc@CNT and Ag@CNT counterparts. This work highlights the synergistic role of metalmolecular heterointerfaces in tandem catalysis, offering an advanced avenue for designing cascade catalysts for CO2 electroreduction.

To address the challenges of noble metal costs and the hydrogen poisoning of single-metal ruthenium (Ru)-based catalysts in ammonia synthesis, a RuCo bimetallic catalyst supported on CeO2 nanorods was prepared in this work. First, a RuCoCe-BTC metal–organic framework precursor, where BTC denotes 1,3,5-benzenetricarboxylate, was obtained by partially substituting Ru with the non-noble metal cobalt (Co), followed by pyrolysis to yield the RuCo/CeO2 catalyst. The formation of Co–Ru bonds, which provided enhanced metal support interactions in this bimetallic catalyst, was confirmed by the blue shift of the Ru–O–Ce vibration peaks in the Raman bands. Compared to a single-metal Ru/CeO2 catalyst, Co doping enhanced the generation of more oxygen vacancies and the reduction of high-valence Ru, leading to promoted hydrogen transfer on the Ru sites. The hydrogen poisoning of Ru sites was suppressed due to H* spillover to the Co sites, which was explained by the higher H2 adsorption energy on Co sites (−0.720 eV) compared to that on Ru sites (−0.367 eV). Consequently, the RuCo/CeO2 catalyst achieved an NH3 synthesis rate of 21.0 mmol/(g·h) at 5 MPa and 400 °C, demonstrating better performance than the Ru/CeO2 catalyst (18.5 mmol/(g·h)).

Abstract Molecularly dispersed cobalt phthalocyanine (CoPc) on carbon nanotubes can be used as an efficient catalyst for electrochemical CO2-to-methanol conversion. However, increasing the CoPc loading to enhance the current density typically induces aggregation, which compromises methanol selectivity. To overcome this limitation, a CNT-supported nitro-substituted CoPc electrocatalyst (nCoPc@CNT) that adopts a distinct molecular-cone configuration was developed in this work, differing from both molecularly dispersed and aggregated structures. Structural analyses confirm that this molecular-cone configuration increases the density of electrochemically accessible sites while maintaining favorable catalytic activity. Combined theoretical and experimental analyses suggest that the molecular-cone architecture establishes an optimized interfacial microenvironment, in which the electric-field enhancement predicted by COMSOL is associated with local K+ enrichment and stabilization of the key *CO intermediate. Concurrently, interfacial water structures are reorganized to form a strengthened hydrogen bond network that promotes proton transport and accelerates *CO hydrogenation kinetics, as evidenced by a shortened DRT low-frequency relaxation time. Leveraging this microenvironment, the molecular-cone nCoPc@CNT catalyst achieves a methanol Faradaic efficiency of 64.4% at –0.98 V vs RHE and retains a Faradaic efficiency of 58.4% at 150 mA cm–2 in a membrane electrode assembly (MEA) cell. This work presents a microenvironment-engineering strategy for selective electrochemical CO2 reduction to methanol via cooperative interfacial tuning.

In response to the mass transfer limitation of low concentration CO2 (approximately 400 ppm) in closed tubular photobioreactors aimed at improving indoor air quality, nanomaterials with excellent hydrolytic stability, OLA@KAUST-7, served as CO2 carriers. This approach sought to enhance carbon sequestration efficiency and biomass accumulation in Chlorella. The experiment examined the effects of varying addition amounts (0.01, 0.05, and 0.1mmol/L) on the growth and physiological metabolism of Chlorella. The results indicated that 0.01mmol/L represented the optimal dosage; at this concentration, the conversion efficiency of algal liquid CO2 to HCO3- increased by 55.7%. Transcriptomic analysis confirmed that the introduction of an appropriate amount of OLA@KAUST-7 significantly upregulated the gene expression of key proteins in the photosystem, such as Lhcb and psbO, as well as core energy metabolism enzymes like gpi and aco. This upregulation synergistically enhanced photochemical energy conversion efficiency and intracellular energy supply. The synthesis capacity of photosynthetic pigments in Chlorella significantly improved, ultimately resulting in a 53.06% increase in biomass yield.

For improving the activity of low-cost non-noble metal catalysts for the oxygen evolution reaction (OER) in acidic water electrolysis, a strategy was proposed to construct atomic Mn-O-Co asymmetric units within Co3O4 to form a directional built-in electric field. Mn-doped Co3O4 catalysts (Mn x Co3-x O4) were synthesized via a hydrothermal-calcination method. The computational results indicated that Mn selectively occupied the octahedral Co site, forming a directional electron transfer pathway from Mn to Co, which effectively modulated the electronic structure of both Co and O. In situ Raman spectroscopy proved that the Mn-O-Co structure accelerated the efficient conversion of oxygen-containing intermediates. DFT calculations indicated that the Mn-O-Co directional built-in electric field facilitated H2O polarization via enhancing hydrogen bonding and, by optimizing the *OOH adsorption structure, lowered the OER rate-determining step barrier by 0.05 eV. The asymmetric Mn-O-Co coordination structure lowered the p-band center of the O atom by similar to 0.1 eV atom, which passivated lattice-O to improve lattice stability. XPS revealed that the Mn0.6Co2.4O4 material had the maximum built-in potential. The electrochemical testing indicated that it exhibited an overpotential of only 243 mV at a current density of 10 mA cm-2 and maintained stability for over 80 h.

To address the lack of genetic tools currently hindering the improvement of methanogens with complex metabolic pathways, Co-60-gamma irradiation was applied to mutate Methanosarcina barkeri, yielding the efficient strain M600. Transcriptomics revealed significant upregulation of key genes (e.g., Mta, frh, and hdr) involved in ATP synthase in M600, synergistically driving metabolic flux in methane synthesis. Intracellular electron-dense granule levels, cytochrome abundance, and related redox-active substance content increased in the mutant, whereas the surface layer thickness decreased. M600 ' s free-charge transfer resistance declined by 24.2%, while area capacitance rose by 19.7%, significantly enhancing electron shuttling and transient storage. Consequently, M600 ' s methane production increased by 99.4% to 10.27 mmol & centerdot;L-1 in the methylotrophic pathway and by 68.4% to 2.29 mmol & centerdot;L-1 in the hydrogenotrophic pathway.

Biochar, with its well-developed pore structure and tunable surface chemistry, has been widely employed for heavy metal adsorption. However, the biochar after adsorption of heavy metals suffers from high risk of secondary pollution and difficulty in resource utilization. This study explores a feasible approach to converting it into an efficient CO2 adsorbent. Heavy metal ions (represented by Ni2+ in this study) are primarily captured via the mesoporous structure of biochar and can be stably anchored to the carbon skeleton after high temperature treatment. This process introduces alkali metal oxide sites on the biochar surface, which were confirmed as chemisorption centers for CO2 by in situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS). Meanwhile, the adsorbed Ni2+ acts as in situ structural template, inducing the evolution of mesopores into narrow micropores, increasing the intermolecular forces between the pore walls and CO2. The synergistic enhancement effect of chemical and physical adsorption significantly improves the CO2 adsorption performance of biochar. The Ni-loaded biochar achieves a CO2 adsorption capacity of 4.49 mmol/g at 25 degrees C and 1 bar, and a CO2/N2 dynamic separation coefficient of 74.47 in multi-component breakthrough experiments. This study provides a green and sustainable approach that combines heavy metal pollution control with the development of CO2 capture materials, delivering dual energy and environmental benefits.

Bismuth-based semiconductor materials exhibit tremendous potential in photocatalytic CO2 reduction reactions (CO2RR) due to their unique layered structure, suitable bandgap, excellent visible-light responsiveness, and photochemical stability. As environmentally friendly photocatalysts, bismuth-based materials have garnered extensive attention for alleviating energy crises and environmental pollution. However, challenges persist in large-scale applications for bismuth-based catalysts, including high photogenerated carrier recombination rates, limited visible-light response ranges, and insufficient photocatalytic activity. This paper systematically reviews recent research progress on bismuth-based catalysts for photocatalytic CO2 reduction, focusing on three categories of bismuth-based materials: Bi, Bi2O3 and BiOX (X = Cl, Br or I). It highlights their respective advantages and disadvantages, along with constructive optimization strategies to enhance catalytic efficiency.

The development of efficient non-precious electrocatalysts for the alkaline hydrogen evolution reaction (HER) is critical for industrial water electrolysis. Herein, an amorphous NiS/crystalline Co3O4 heterostructure (NiS/ Co3O4@CP) is fabricated through a scalable two-step electrodeposition. The heterogeneous interface induces electron transfer from Co3O4 to NiS, creating electron-rich NiS sites for optimized H* adsorption/desorption and high-valence Co3+ species for accelerated water dissociation. The NiS/Co3O4@CP catalyst exhibits low overpotential of 60 mV at 10 mA cm- 2 in 1 M KOH (25 degrees C) and maintains durability for 1000 h. Under industrial conditions (80 degrees C, 6 M KOH), the NiS/Co3O4@CP also exhibits an overpotential of merely 285 mV at 500 mA cm- 2. In a two-electrode electrolyzer, the NiS/Co3O4@CP//Ni mesh configuration attains a current density of 500 mA cm- 2 at a voltage of merely 1.9 V. This work provides a practical strategy for high-performance HER catalysts.

The CO2 hydrogenation to methanol reaction is limited by chemical equilibrium, resulting in a low single-pass CO2 conversion. This paper reviewed three methods of condensation, adsorption, and membrane separation to separate water byproduct and methanol product for overcoming chemical equilibrium limitations. Dividing methanol synthesis reactor into 2–3 stages with intermediate condensation of products (water and methanol) is easier to operate with a high CO2 conversion than sorption-enhanced methanol synthesis process, and it consumes relatively little energy. Water removal by adsorbents mixed with catalysts consumes much energy for repressurization and purging, and sorption-enhanced process operated in a non-steady state for regenerating adsorbents lowers methanol production rate. Packed bed membrane reactors have low power consumption, but cost a bit more compared to multi-stage condensation due to complicated configuration. In summary, multi-stage methanol synthesis with intermediate condensation is the most cost-efficient method to overcome chemical equilibrium limitations for improving CO2 conversion in industrial production.

Rational modulation of the Cu-ZnO interfaces by modifying Layered Double Hydrotalcite (LDH) with additives the provides a promising way for enhanced methanol production from CO2, while the extent to which the promoters contribute to the topological transformation process of LDH and the reaction pathway remains unexplored. Herein, a LDH-derived CuZnAl catalyst with manganese (Mn) promoter modification is designed for efficient CO2-to-methanol production. Compared with amorphous catalysts, at 260 degrees C and 5 MPa, the asoptimized CuZnAlMn-LDO exhibits a CO2 conversion of 23.03% with a STYMeOH of 584.15 gMeOH center dot kgcat Characterizations conform that the introduction of Mn content directly involves in the formation of LDH and boost the thermal stability of the LDH morphology, resulting in the reservation of LDH nanosheet structure with lower thickness and higher surface area after calcination. These modifications effectively trigger stronger electron transfer and boost the formation of Cu-ZnO interfaces for enhanced CO2 adsorption. Moreover, smaller and more dispersed Cu species were also observed on CuZnAlMn-LDO, effectively facilitating H2 dissociation. In-situ tests further demonstrate that the formation of formate and its further hydrogenation are accelerated. This work highlights that tuning the topological transformation of LDH structure could effectively regulate metal-support interaction to enrich Cu-ZnO interfaces for enhanced performances.

Abstract Cu-based catalysts are promising for CO2-to-methanol conversion, but their activity and stability are usually compromised by the accumulation of byproduct water. Although physically mixing hydrophobic additives with Cu-based catalysts can facilitate water removal, how to regulate the water-removal kinetics in this process, as well as its impact on the reaction kinetics of CO2 hydrogenation to methanol, remains insufficiently understood. Herein, by modifying the polydivinylbenzene (PDVB) with porosity, we regulate the surface hydrophobicity of its mixture with a layered double hydroxide (LDH)-derived CuZnAlMg catalyst, thereby enhancing the water removal kinetics on the mixed catalyst surface. In contrast to nonporous PDVB, porous PDVB, with a substantially higher surface area and abundant mesopores, effectively creates additional H2O transfer channels. This facilitates rapid water removal, which in turn inhibits the oxidation of Cu nanoparticles and ensures the re-exposure of oxygen-vacancy active sites for sustained catalysis. Furthermore, water removal also accelerates the formation and subsequent hydrogenation of intermediates for higher activity. Consequently, a high space-time yield of methanol of 519.89 gMeOH kgcat–1 h–1 and a CO2 conversion rate of 26.35% are achieved at 5 MPa and 260 °C. The mixed catalyst exhibits excellent stability over 200 h of continuous operation. This work offers a simple yet robust strategy for regulating catalyst hydrophobicity toward efficient CO2 hydrogenation to methanol.

The sluggish kinetics of the oxygen reduction reaction (ORR) remains a critical limitation for green energy conversion technologies. Although Fe-N-C single-atom catalysts offer high atomic utilization, their symmetric coordination environments limit electronic flexibility and catalytic activity. Herein, a precoordination-mediated active center evolution strategy is developed to construct dual scale cluster-single atom Fe-Nx active centers using municipal sludge as a low-cost precursor. During the citric acid-assisted hydrothermal process, protein hydrolysis induces the release and redistribution of nitrogen-containing species, forming a precoordinated environment that enables the formation of subnanometer clusters and isolated single-atom sites. Subsequent activation removes mineral species and constructs a hierarchical porous carbon framework with high specific surface area and enhanced mass transport. Density functional theory calculations reveal that electronic coupling between clusters and single atoms induces long-range electronic modulation, shifting the d-band center and optimizing the adsorption energetics of oxygen intermediates. As a result, the catalyst exhibits excellent ORR activity across a wide pH range, delivering a half-wave potential of 0.86 V in alkaline media and outperforming Pt/C in acidic and neutral electrolytes. A Zn-air battery achieves a peak power density of 195 mW cm-2, while microbial fuel cells deliver 1589 mW m-2 with 54% pollutant degradation. Life-cycle assessment indicates reduced carbon emissions compared with sludge incineration. This work provides a controllable strategy for constructing dual-scale active centers and highlights their promise in green energy conversion and nano-enabled electrocatalysis.