ACS Sustainable Chemistry & Engineering
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2026
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IF 7.6
Bowen Li,Shuang Zheng,Guilin Li,Jiang Chang,Lu Bai,Yinge Bai,Xiangping Zhang,Shaojuan Zeng
To address the growing demand for efficient low-concentration CO2 capture from flue gas, functionalized ionic liquid (IL) hybrids─integrating ILs’ intrinsic CO2-philicity (specific functional group-CO2 interactions) and porous supports’ structural merits (high specific surface area, tunable pores, robust framework)─have emerged as promising adsorbents. In this work, a kind of novel polyamine IL (PIL) hybrid with narrowly distributed mesopores and ultrahigh IL loading over 70 wt % was fabricated by immobilizing the PIL triethyltetramine trifluoromethanesulfonate ([TETA][TfO]) onto a hydrophobic resin (XAD) featuring wide mesopores and a small fraction of macropores. At 313 K, 70 wt % [TETA][TfO]@XAD exhibited a high CO2 adsorption capacity of 3.09 mmolCO2/g-adsorbent at 1 bar and 2.35 mmol CO2/g-adsorbent at 0.15 bar. Notably, under simulated humid flue gas conditions (15 vol % CO2/5 vol % H2O balanced with N2), the PIL hybrid still could maintain a relatively stable adsorption capacity of 1.31 mmol CO2/g-adsorbent, which is comparable to that under dry flue gas conditions (1.24 mmol CO2/g-adsorbent, 15 vol % CO2 balanced with N2). Furthermore, after three consecutive adsorption–desorption cycles, the PIL hybrid maintained structural integrity and stable CO2 adsorption performance without significant attenuation under both dry and humid environments. The superior CO2 separation performance was attributed to the chemical interactions between CO2 and multiple amino groups (one secondary amine as well as two primary amines) of [TETA]+, coupled with the synergistic effect of the in situ-formed mesoporous structures. This work provides a feasible strategy for the rational design and development of mesoporous PIL hybrids for the efficient capture of low-concentration CO2 from flue gas.
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CHEMICAL ENGINEERING SCIENCE
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2026
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IF 5.1
Xin Li,Jiping Mu,Yibo Fu,Xiaofang Su,Zhenzhen Wang,Zhiyong Li
The separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) and its subsequent storage remain formidable challenges in the petrochemical industry due to their nearly identical kinetic diameters and similar physical properties, which render conventional adsorption methods inefficient. Herein, we report an anion-pillared ultra-microporous metal–organic framework, Ni-TiF 6 -T4PP, engineered with tailored pore geometry and selective binding sites to achieve efficient C 2 H 2 /CO 2 separation. This material exhibits a high C 2 H 2 uptake of 3.99 mmol g −1 at 298 K and 1 bar. The pore environment, enriched with nitrogen and fluorine sites, promotes host–guest interactions with C 2 H 2 , resulting in a substantial differential in the isosteric heats of adsorption (Q st ): 36.04 kJ mol −1 for C 2 H 2 versus 19.35 kJ mol −1 for CO 2 . Combined with its low regeneration energy barrier, the framework can be readily regenerated, contributing to its recyclability. Breakthrough experiments demonstrate achieves separation performance for equimolar C 2 H 2 /CO 2 mixtures. At 353 K, a C 2 H 2 mixture with an initial concentration of 90% can be purified to achieve a final purity of > 99.2%. Based on the combined evidence from in situ infrared spectroscopy and molecular simulation, the underlying gas adsorption mechanism has been conclusively established that the extended π-surfaces of porphyrin and pyridine moieties enable multipoint cooperative binding with C 2 H 2 .
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Journal of CO2 Utilization
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2026
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IF 8.6
Ruifeng Zhou,Muhammad Shuaib Khan,Xianwei Fu,Qiuye Li
The extensive utilization of fossil fuels has accelerated greenhouse gas emissions, triggering climate issues that have become a global concern. The integration of waste valorization with CO 2 capture agent development is recognized as a green, cost-effective, and efficient approach to achieving carbon neutrality and environmental protection. In this study, porous SiO 2 supports (specific surface area 809.35 m 2 /g) are fabricated from coal-fired power plant waste (fly ash) to synthesize a series of co-modified amine-functionalized adsorbents for CO 2 capture. Through a strategic combination of KH550 (Aminopropyltriethoxysilane) hydrolytic grafting and PEHA (Pentaethylenehexaamine) wet impregnation, a polyamine network is constructed, endowing the co-modified adsorbent CS-4K 50PEHA with superior CO 2 uptake (4.933 mmol/g, 70℃) and exceptional thermal stability. Thermogravimetric-infrared analysis and DFT calculations confirmed the chemical bonding of KH550 to the support, with the co-modified adsorbent exhibiting enhanced thermal stability (thermal decomposition temperature 320℃) compared to singly-modified counterparts. Furthermore, the structure-activity relationship between silane coupling agents and the support during hydrolysis is systematically investigated. The synergistic effect of polyamine active sites on the CO 2 adsorption mechanism is elucidated through in situ DRIFTS and DFT simulations. This work provides molecular-level insights into different amine modification strategies for solid waste-based supports, highlighting the significance of cooperative adsorption mechanisms at the intersection of waste valorization and carbon capture technologies.
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APPLIED SURFACE SCIENCE
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2026
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IF 6.6
Rongjing Jia,Shuling Chang,Ruirui Wang,Yanhong Xu,Rijie Wang,Lihong Zhang
The electrocatalytic CO 2 reduction reaction to CO (ECO 2 RR) is an effective way to achieve carbon resource utilization. It requires catalysts that can synergistically couple CO 2 activation with efficient CO desorption. This work engineers this synergy by constructing an interfacial Ag δ+ -O-Zn configuration on Zn(OH)F-derived supports via controlled Ag loading (0–5 wt%). The optimal catalyst (3A/Z, 3 wt% Ag) balances the formation of interfacial, oxidized Ag species (Ag δ+ ) with well-dispersed metallic Ag 0 nanoparticles. It achieves a CO Faradaic efficiency of 95.4% at −1.15 V vs. RHE and maintains 86% efficiency over 5 h at 6.38 mA cm −2 . In-situ ATR-SEIRAS spectra and kinetics reveal that Ag δ+ -related sites lower the barrier for *COOH formation, while adjacent Ag 0 domains facilitate *CO desorption. Excessive loading (5A/Z) promotes Ag aggregation and support decomposition, diminishing the critical Ag δ+ -O-Zn interface and performance. This study highlights interface coordination engineering as a key strategy for designing bifunctional ECO 2 RR catalysts.
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iScience
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2026
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IF 4.5
Qixian xie,Bowen Guo,Yichen Zhang,Tianze Yang,Chenfang Cui,Zhengliang Liu,Honglin Yao,Baili Li,Wurong Ren
The integration of the KHCO 3 fed bipolar membrane (BPM) electrolyzer with KOH based CO 2 capture enables directly in situ conversion of captured CO 2 into valuable carbonaceous products, eliminating costly CO 2 recovery and compression steps. Even this integrated BPM system assembly holds promise, the critical lack of CO 2 adsorption intermediate species tracking necessitates the development of a monitoring platform. This work pioneers a novel dual-modal strategy employing simultaneous indicator-based sensing with in situ UV-Vis spectroscopy, achieving real time visualization of triphasic dynamics during integrated CO 2 capture-regeneration-conversion. Within this synergistic process involving Ar-saturated KHCO 3 decomposition, and electrochemical reduction, an etched indium (In) catalyst achieves 50% formate Faradaic efficiency (FE) at -1.1 V vs. RHE. The synergistic application of these complementary in situ diagnostics unlocks fundamental mechanistic insights into integrated CO 2 capture and conversion systems, establishing them as critical enablers for advancing efficient and scalable electrochemical CO 2 valorization.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
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IF 19.7
Qi Qin,Cheng-Yi Huang,Zhi-Hua Xia,Wei-Qi Liu,Hong-Yan Chen,Dai-Bin Kuang
Rational modulation of interfacial electronic structure has been regarded as an appealing strategy to achieve effective charge separation and synergistic active-site cooperation in heterojunction photocatalysts, yet it remains a significant challenging. In this study, two-dimensional (2D) vinylene-linked conjugated covalent organic polymer (COP) functionalized with –F and –CN groups was designed through Knoevenagel condensation reaction. The influence of these groups on the interfacial properties and the photocatalytic performances of Cs 3 Sb 2 Br 9 /COP heterojunction were investigated systematically. Combined experimental and theoretical calculations revealed that introducing strong electron-withdrawing groups improves charge separation by inducing strong electron delocalization within the COP framework, enhances CO 2 adsorption and activation, and most importantly, significantly facilitates the interfacial growth of Cs 3 Sb 2 Br 9 nanocrystals. It was found that the strengthened interfacial interaction via Sb─N bonding effectively promoted a fast Z-scheme charge transfer and enabled effective spacial separation of photoelectron and holes, in contrast to the type II mechanism observed in the un-functionalized heterojunction. This enables effective multifunctional collaboration of Cs 3 Sb 2 Br 9 and FN-COP. Consequently, the optimized Cs 3 Sb 2 Br 9 /FN-COP heterojunction achieved a total electron rate of 135.42 µmol·g -1 ·h -1 for CO 2 reduction coupled with a benzaldehyde production rate of 179.73 µmol·g -1 ·h -1 , representing a 2.4 and 2.6-fold enhancement over the un-functionalized heterojunction. This work demonstrates a novel "molecular engineering–interface modulation–function cooperation" strategy to construct high-quality heterojunction precisely, providing valuable insights for the design of high-performance photocatalysts for next-generation energy conversion applications.
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CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Meng Qiao,Yan-Fei Mu,Ji-Li Zhou,Su-Xian Yuan,Meng-Ran Zhang,Min Zhang,Tong-Bu Lu
Cu optimizes Co 3 O 4 d-orbital occupancy for symmetry-matched interactions with N 2 and CO 2 . • Cu-Co 3 O 4 reduces C − N coupling barrier from 2.34 to 1.19 eV. • Cu-Co 3 O 4 exhibits superior performance, ranking among the highest reported for photocatalytic urea synthesis. Photocatalytic CO 2 /N 2 co-reduction to urea is a green route for carbon‑nitrogen cycle closure, yet it is severely limited by the disparate orbital symmetry requirements of CO 2 /N 2 that impede synergistic activation on a single catalyst. Herein, Co 3 O 4 is doped with Fe/Cu/Ni to tailor the d -orbital configuration of its active sites, and Cu-Co 3 O 4 emerges as the optimal catalyst. It delivers a high urea yield of 25 μmol g −1 h −1 and a solar-to-urea conversion efficiency of nearly 0.035%, which ranks among the top efficiencies for photocatalytic urea synthesis. In situ diffuse reflectance infrared Fourier transform spectroscopy identifies *N 2 CO as the key reaction intermediate, while projected density of states calculations reveal that Cu 2+ ( d 9 ) optimizes d orbital occupation of catalyst to realize symmetry-matched adsorption of CO 2 /N 2 and strengthen orbital coupling. Density functional theory calculations further demonstrate that *N 2 CO formation is the rate-limiting step for urea synthesis, with Cu-Co 3 O 4 lowering the C − N coupling barrier to 1.19 eV (vs. 2.34 eV for pristine Co 3 O 4 ). This work establishes orbital symmetry matching between the d -orbitals of catalytically active sites and the π orbitals of reactants as a critical determinant for the selectivity of multi-molecule co-reduction reactions, thereby providing a general design principle for the development of high-performance photocatalysts. A Cu-doped Co 3 O 4 photocatalyst is rationally engineered, where incorporated Cu 2+ ( d 9 ) optimizes the occupation of active d xy / d xz orbitals in Co 3 O 4 , enabling symmetry-matched interactions with CO 2 and N 2 and reducing the C − N coupling barrier. This catalyst achieves a high urea yield of 25 μmol g −1 h −1 and a solar-to-urea conversion efficiency of ~0.035%, ranking among the top-performing systems for photocatalytic urea synthesis to date. Download: Download high-res image (115KB) Download: Download full-size image
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
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IF 19.7
Fengyi Zhong,Chenyu Du,Jianping Sheng,Ye He,Majid Moghadam,Fan Dong,Yanjuan Sun
Hot carrier-lattice coupling driven by Br migration defects is identified as the intrinsic origin of CsPbBr 3 PNCs instability. • An In-anchoring strategy suppresses Br migration, passivates defects, and prolongs the hot carrier lifetime by ∼99%. • In-anchored CsPbBr 3 PNCs achieves a cumulative CO yield of 2.2 mmol g –1 over 60 h , 14.85 times higher than CsPbBr 3 PNCs. CsPbBr 3 perovskite nanocrystals (PNCs) demonstrate exceptional photocatalytic potential in CO 2 conversion through superior light harvesting and multi-exciton generation. However, their practical application is fundamentally hindered by structural instability that compromises carrier utilization. This study, using femtosecond transient absorption spectroscopy and temperature-dependent photoluminescence, reveals that dynamic coupling between hot carriers and lattice vibrations drives structural degradation via localized phonon excitations. To address this, we engineered indium (In)-anchored CsPbBr 3 PNCs by targeted modification of surface Pb centers. The In-anchoring passivates defect-associated empty p-orbitals while prolonging the hot carrier lifetime by 98.86%. Furthermore, the introduced In ions induce electronic localization, which suppresses phonon-driven lattice vibrations. As a result, charge separation and transport are dramatically enhanced, leading to a significant improvement in both CO 2 reduction activity and stability. In contrast to CsPbBr 3 PNCs, which completely deactivate within 20 h, In-anchored CsPbBr 3 PNCs maintain stability over long-term operation for up to 60 h, while simultaneously exhibiting a 14.85-fold enhancement in CO yield. This study establishes a fundamental strategy for stabilizing perovskite photocatalysts by regulating hot carrier-lattice interactions, offering new insights into the design of high-performance CO 2 reduction systems. Download: Download high-res image (188KB) Download: Download full-size image This work establishes an indium-anchoring strategy that regulates carrier-lattice interactions, suppresses defect-induced degradation, prolongs hot-carrier lifetime, and simultaneously enhances the photocatalytic activity and stability of CsPbBr 3 perovskite nanocrystals.
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JOURNAL OF RARE EARTHS
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2026
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IF 9.6
Siqi Liu,Zhaoliang Wu,Yuanrui Li,Jun Yu,Lei Zhang
Electrocatalytic CO 2 reduction reaction (CO 2 RR) provides a sustainable route for transforming CO 2 into value-added chemicals, yet achieving controllable selectivity remains a major challenge. Here, we constructed Ce-rich and Cu-rich Ce-Cu interfaces (CeCu 0.55 O x and CeCu 2.67 O x ) to elucidate the interfacial regulation of CO 2 RR pathways. CeCu 0.55 O x delivers a CH 4 Faradaic efficiency (FE) of 45% at –400 mA/cm 2 , whereas CeCu 2.67 O x achieves over 50% FE toward C 2 products. Operando Raman measurements reveal comparable Cu oxidation states during CO 2 RR, indicating that interfacial composition rather than Cu valence dominates selectivity. The Ce-rich interface accelerates H 2 O dissociation, increasing *H coverage and promoting sequential hydrogenation of *CO to CH 4 . In contrast, the Cu-rich interface strengthens *CO adsorption and increases its surface coverage, steering C−C coupling toward *OC-CO and enabling C 2 product formation. This work clarifies how tuning the Ce/Cu ratio modulates *H and *CO intermediate coverages, providing a mechanistic basis for designing oxide-metal interfaces with programmable CO 2 RR selectivity.
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ACS Catalysis
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2026
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IF 13.6
Yong Chen,Wenlong Wang,Rengui Li,Haoyang Yuan,Hao Ren,Jining Zhang,Jing Zhang
Photocatalytic CO2 reduction using H2O as the sole electron and proton source represents the ultimate challenge in artificial photosynthesis, yet it is severely hindered by the sluggish kinetics of CO2 adsorption and activation processes. Herein, we report a rationally designed photocatalyst comprising Ru-decorated In2O3 nanorods enriched with surface hydroxyl groups and oxygen vacancies (In2O3−x(OH)y), which drives the conversion of CO2 and H2O into CO and CH4 without sacrificial agents. Atomic-level structural design creates surface frustrated Lewis pairs (FLPs) through the synergy between coordinately unsaturated In sites (Lewis acids) and adjacent In−OH groups (Lewis bases). These FLP sites drastically enhance CO2 adsorption and facilitate its polarization and activation. Meanwhile, Ru nanoparticles not only facilitate electron extraction from the In2O3−x(OH)y nanorods but also function as “nanoheaters” that rapidly raise the local temperature to accelerate water vaporization. The synergistic cooperation between FLPs and Ru cocatalysts fosters balanced and efficient redox kinetics. Consequently, the optimized photocatalyst achieves markedly enhanced CO and CH4 production rates that are 40 and 31 times higher than those of pristine In2O3, respectively, while achieving stoichiometric O2 evolution. This work underscores the pivotal role of surface FLPs and provides a fundamental principle for constructing efficient sacrificial-agent-free photocatalytic systems.
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INORGANIC CHEMISTRY
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2026
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IF 4.6
Xue-Rong Dou,Xin-Yue Zheng,Yun-Nan Gong,Di-Chang Zhong,Tong-Bu Lu
The performance of photocatalytic CO2 reduction is highly dependent on the electronic structures of active sites, while achieving delicate regulation of electronic states to enhance the catalytic performance remains challenging. Herein, we designed and synthesized four salen cobalt complexes with different functional groups in organic ligands (Co-X, X = –NO2, −COOMe, -tBu, and -OMe) for photocatalytic CO2 reduction. Impressively, by changing the -X groups of the organic ligands, the electronic structures of Co ions in Co-X can be regulated, which results in obviously different photocatalytic performance for the reduction of CO2 to CO, following the -X group sequence of –NO2 > −COOMe > -tBu > -OMe. The optimized Co–NO2 with the strongest electron-withdrawing ability of the –NO2 group achieves the largest turnover number (TON) and turnover frequency (TOF) values of 5727 and 0.32 s–1, respectively, 4.5 times higher than those of the Co–OMe. Theoretical calculations reveal that the spin populations of Co in Co–NO2 are the largest among the four cobalt complexes, which is the most beneficial for absorbing and activating the CO2 molecule, thereby accounting for its highest photocatalytic activity.
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ACS Sustainable Chemistry & Engineering
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2026
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IF 7.6
Hong-Mei Jiang,Jian Sheng,Shu-Zhen Zhou,Hang Yao,Fan Tang,Dongqi Wang
Developing high-performance, non-precious-metal catalysts that operate efficiently at low temperatures remains a pivotal challenge for CO2 methanation, particularly for systems with high active metal loadings where nanoparticle sintering often compromises performance. Herein, Mn-promoted Ni/ZrO2 catalysts with 40 wt % Ni were prepared via a Pechini method, demonstrating exceptional low-temperature performance. Under atmospheric pressure, the optimized 5Mn–Ni/ZrO2 catalyst achieved stable 70% CO2 conversion, near-100% CH4 selectivity, and a stable CH4 yield of 150 mmol/g/h for 117 h at 225 °C. Comprehensive characterization (XRD, TEM, XPS, H2-TPR, CO2-TPD, H2-TPD) revealed that Mn doping facilitates NiO reduction with higher Ni dispersion, increases electron density on Ni sites, and increases the population of medium-strength basic sites and oxygen vacancies on the ZrO2 support. These synergistic modifications collectively promote CO2 adsorption, H2 adsorption, and catalyst reducibility. In situ DRIFTS further identified a formate-mediated pathway, in which Mn promotes the stabilization and subsequent hydrogenation of the HCOO* intermediate. This work demonstrates that rational exploitation of promoter-support synergy can overcome the dispersion limitations inherent to high-loading Ni catalysts, providing an effective design strategy for advanced, low-temperature CO2 methanation catalysts.
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