Photothermal catalytic dry reforming of methane (DRM) offers a sustainable route for carbon conversion but suffers from kinetic imbalance between CH4 and CO2 activation. To address the fundamental challenge, we design a bifunctional NiRu-MgO/MgAl2O4 catalyst, where the metal alloy and basic oxide support are tailored to synergistically activate CH4 and CO2, respectively. The balanced activation enables exceptional and stable performance under high-throughput conditions, and the optimized catalyst achieved CO2 and CH4 conversion rates of 91.3% and 80.9%, respectively, with stable operation for 50 h at a high gas hourly space velocity of 360 L h−1 g−1. Mechanistic studies reveal that the superior performance originated from a novel light-induced reaction pathway via a key CH3O* intermediate. The work underscores that engineering matched activation on bifunctional sites, powered by photothermal synergy, is a key design principle for efficient and stable DRM catalysis under practical conditions.
光热催化甲烷干重整（DRM）为碳转化提供了一条可持续的途径，但存在CH4和CO2活化动力学不平衡的问题。为了解决这一根本性的挑战，我们设计了一种双功能的nru - mgo /MgAl2O4催化剂，其中金属合金和碱性氧化物载体分别用于协同激活CH4和CO2。平衡活化使催化剂在高通量条件下具有优异而稳定的性能，优化后的催化剂CO2和CH4的转化率分别为91.3%和80.9%，在360 L h−1 g−1的高气时空速下稳定运行50 h。机理研究表明，这种优越的性能源于一种新的光诱导反应途径，该途径通过一个关键的ch30 *中间体。这项工作强调了在双功能位点上的工程匹配激活，由光热协同作用驱动，是在实际条件下高效和稳定的DRM催化的关键设计原则。
{"title":"Engineering matched activation on a bifunctional NiRu catalyst for efficient photothermal dry reforming of methane","authors":"Zhijia Yang, Yao Xue, Yujun Wang, Ruoyu Wang, Molly Meng-Jung Li, Xiao-Jue Bai, Yufei Zhao","doi":"10.1002/aic.70326","DOIUrl":"https://doi.org/10.1002/aic.70326","url":null,"abstract":"Photothermal catalytic dry reforming of methane (DRM) offers a sustainable route for carbon conversion but suffers from kinetic imbalance between CH<sub>4</sub> and CO<sub>2</sub> activation. To address the fundamental challenge, we design a bifunctional NiRu-MgO/MgAl<sub>2</sub>O<sub>4</sub> catalyst, where the metal alloy and basic oxide support are tailored to synergistically activate CH<sub>4</sub> and CO<sub>2</sub>, respectively. The balanced activation enables exceptional and stable performance under high-throughput conditions, and the optimized catalyst achieved CO<sub>2</sub> and CH<sub>4</sub> conversion rates of 91.3% and 80.9%, respectively, with stable operation for 50 h at a high gas hourly space velocity of 360 L h<sup>−1</sup> g<sup>−1</sup>. Mechanistic studies reveal that the superior performance originated from a novel light-induced reaction pathway via a key CH<sub>3</sub>O* intermediate. The work underscores that engineering matched activation on bifunctional sites, powered by photothermal synergy, is a key design principle for efficient and stable DRM catalysis under practical conditions.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"269 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bernard T. Agyeman, Zhe Li, Ilias Mitrai, Prodromos Daoutidis
This work introduces an end-to-end graph-based agent for accelerating the computational efficiency of Benders Decomposition. The agent's policy is parameterized by a graph neural network, which takes as input a bipartite graph representation of the master problem and proposes a candidate solution. The agent is trained using a two-stage approach that combines imitation learning (IL) and reinforcement learning (RL). IL is used to mimic a solver and obtain a warm-start policy, which is then finetuned using RL with a reward signal that balances feasibility and computational efficiency. We augment the agent with a verification mechanism that checks the agent's prediction for feasibility and solution quality. The framework is evaluated in two case studies: (i) an illustrative mixed-integer nonlinear program, where it reduces the solution time by 42% without loss of solution quality, and (ii) a closed-loop irrigation scheduling problem, where it achieves a 23% time reduction without compromising water use efficiency.
{"title":"Graph-based imitation and reinforcement learning for efficient Benders decomposition","authors":"Bernard T. Agyeman, Zhe Li, Ilias Mitrai, Prodromos Daoutidis","doi":"10.1002/aic.70342","DOIUrl":"https://doi.org/10.1002/aic.70342","url":null,"abstract":"This work introduces an end-to-end graph-based agent for accelerating the computational efficiency of Benders Decomposition. The agent's policy is parameterized by a graph neural network, which takes as input a bipartite graph representation of the master problem and proposes a candidate solution. The agent is trained using a two-stage approach that combines imitation learning (IL) and reinforcement learning (RL). IL is used to mimic a solver and obtain a warm-start policy, which is then finetuned using RL with a reward signal that balances feasibility and computational efficiency. We augment the agent with a verification mechanism that checks the agent's prediction for feasibility and solution quality. The framework is evaluated in two case studies: (i) an illustrative mixed-integer nonlinear program, where it reduces the solution time by 42% without loss of solution quality, and (ii) a closed-loop irrigation scheduling problem, where it achieves a 23% time reduction without compromising water use efficiency.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"53 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147384030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Direct conversion of CO2 toward isomerized heavy olefins remains a challenge. In this work, Fischer-Tropsch synthesis and light olefins oligomerization were coupled to produce isomerized heavy olefins from CO2 hydrogenation on a bifunctional K/Fe2N-xM/ASA catalyst. A K/Fe2N-17.0%Ga/ASA achieved the highest selectivity (47.7%) toward C4+ heavy olefins, among which the selectivity of isomerized olefins was as high as 32.2%. Ga species did not adsorb light olefins (e.g., ethylene) directly, but they boosted the adsorption of light olefins on ASA support. Besides, the addition of Ga promoted H2 dissociation to generate Ga-H species, which further transferred onto ASA support to form additional Brønsted acid sites promoting oligomerization reaction that obeyed β-H elimination mechanism via alkoxide intermediates. This work developed not only a unique K/Fe2N as Fischer-Tropsch synthesis catalyst, but also an integrated system coupling Fischer-Tropsch synthesis and light olefins oligomerization to achieve high selectivity isomerized heavy olefins synthesis from CO2 hydrogenation.
{"title":"Direct hydrogenation of CO2 to C4+ isomerized olefins on a K/Fe2N-xGa/ASA bifunctional catalyst","authors":"Bingbing Liao, Fei Chen, Lingyu Jia, Shanshan Dang, Weifeng Tu, Zhenzhou Zhang, Yifan Han","doi":"10.1002/aic.70355","DOIUrl":"https://doi.org/10.1002/aic.70355","url":null,"abstract":"Direct conversion of CO<sub>2</sub> toward isomerized heavy olefins remains a challenge. In this work, Fischer-Tropsch synthesis and light olefins oligomerization were coupled to produce isomerized heavy olefins from CO<sub>2</sub> hydrogenation on a bifunctional K/Fe<sub>2</sub>N-<i>x</i>M/ASA catalyst. A K/Fe<sub>2</sub>N-17.0%Ga/ASA achieved the highest selectivity (47.7%) toward C<sub>4+</sub> heavy olefins, among which the selectivity of isomerized olefins was as high as 32.2%. Ga species did not adsorb light olefins (e.g., ethylene) directly, but they boosted the adsorption of light olefins on ASA support. Besides, the addition of Ga promoted H<sub>2</sub> dissociation to generate Ga-H species, which further transferred onto ASA support to form additional Brønsted acid sites promoting oligomerization reaction that obeyed β-H elimination mechanism via alkoxide intermediates. This work developed not only a unique K/Fe<sub>2</sub>N as Fischer-Tropsch synthesis catalyst, but also an integrated system coupling Fischer-Tropsch synthesis and light olefins oligomerization to achieve high selectivity isomerized heavy olefins synthesis from CO<sub>2</sub> hydrogenation.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"6 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Layered transition metal oxides (LTMOs, e.g., NaxNiyMn1−yO2) are critical cathode materials for sodium-ion batteries (SIBs). However, they grapple with significant structural degradation during cycling, primarily caused by micro-strain induced by TM heterogeneity during synthesis. Herein, we engineered a vortex microreactor to intensify fluid mixing during co-precipitation processes, thereby achieving carbonate precursors with highly uniform elemental distribution. CFD simulations revealed fundamental microreactor hydrodynamics. Villermaux–Dushman experiments confirmed ≤0.62 ms molecular-scale mixing, achieving near-complete homogenization. The resulting precursors enabled exceptionally uniform TM distribution, yielding a P2-type LTMO cathode with outstanding Ni/Mn homogeneity. Comparing with ball milling synthetics, this cathode exhibits superior rate capability, delivering an impressive 77.51 at 3000 mA g−1 while retaining 90% of the capacity measured at 150 mA g−1. This work establishes micromixing engineering as a critical lever for inducing uniform TM distribution in LTMOs and provides a scalable platform for preparing SIBs cathode materials.
层状过渡金属氧化物（LTMOs，如NaxNiyMn1−yO2）是钠离子电池（sib）的关键正极材料。然而，它们在循环过程中面临着显著的结构降解，这主要是由合成过程中TM非均质性引起的微应变引起的。在此，我们设计了一个涡流微反应器来加强共沉淀过程中的流体混合，从而获得元素分布高度均匀的碳酸盐前驱体。CFD模拟揭示了基本的微反应堆流体力学。Villermaux-Dushman实验证实了≤0.62 ms的分子尺度混合，实现了近乎完全的均质化。所得到的前驱体使TM分布异常均匀，产生具有优异Ni/Mn均匀性的p2型LTMO阴极。与球磨合成材料相比，该阴极表现出卓越的倍率能力，在3000 mA g - 1下提供了令人印象深刻的77.51，同时保持了150 mA g - 1下测量的90%的容量。这项工作建立了微混合工程作为诱导LTMOs中均匀TM分布的关键杠杆，并为制备SIBs阴极材料提供了可扩展的平台。
{"title":"Unveiling flow and mixing mechanism of a vortex microreactor and its use in preparing uniform layered oxide materials","authors":"De-Ming Chen, Yan-Jiang Liu, Shi-Xiao Wei, Ting-Liang Xie, Shuang-Feng Yin","doi":"10.1002/aic.70345","DOIUrl":"https://doi.org/10.1002/aic.70345","url":null,"abstract":"Layered transition metal oxides (LTMOs, e.g., Na<sub><i>x</i></sub>Ni<sub><i>y</i></sub>Mn<sub>1−<i>y</i></sub>O<sub>2</sub>) are critical cathode materials for sodium-ion batteries (SIBs). However, they grapple with significant structural degradation during cycling, primarily caused by micro-strain induced by TM heterogeneity during synthesis. Herein, we engineered a vortex microreactor to intensify fluid mixing during co-precipitation processes, thereby achieving carbonate precursors with highly uniform elemental distribution. CFD simulations revealed fundamental microreactor hydrodynamics. Villermaux–Dushman experiments confirmed ≤0.62 ms molecular-scale mixing, achieving near-complete homogenization. The resulting precursors enabled exceptionally uniform TM distribution, yielding a P2-type LTMO cathode with outstanding Ni/Mn homogeneity. Comparing with ball milling synthetics, this cathode exhibits superior rate capability, delivering an impressive 77.51 at 3000 mA g<sup>−1</sup> while retaining 90% of the capacity measured at 150 mA g<sup>−1</sup>. This work establishes micromixing engineering as a critical lever for inducing uniform TM distribution in LTMOs and provides a scalable platform for preparing SIBs cathode materials.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"8 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Model development for bio-alcohol recovery via pervaporation (PV) membranes has been hindered by insufficient molecular-level transport insights. We conducted molecular dynamics simulations to unravel the transport mechanism of solvent (water and alcohol) molecules in polymer membranes. For membranes with different hydrophobicity, alcohol concentrations at both solution-membrane and vapor–liquid interfaces were similar and approximated the activity in aqueous solution. We developed a thermodynamic cycle method for calculating interaction parameters and applied Flory-Huggins theory to quantify the solubility of solvent molecules. In dilute alcohol solutions (≤5 wt%), low solubility promotes molecular-level dispersion of solvent molecules in membranes, making diffusion coefficients nearly solubility independent. Based on these molecular-level insights, the factors affecting the separation factor/relative volatility of PV/distillation processes were quantified using proposed coefficients. These coefficients provide an intuitive understanding of why the separation factor of various polymer membranes is higher or lower than the relative volatility.
{"title":"A computational study on molecular transport mechanisms and models for alcohol recovery by polymer pervaporation membranes","authors":"Shen-Hui Li, Li-Hao Xu, Hao Qi, Ying-Nan Feng, Zhi-Ping Zhao","doi":"10.1002/aic.70346","DOIUrl":"https://doi.org/10.1002/aic.70346","url":null,"abstract":"Model development for bio-alcohol recovery via pervaporation (PV) membranes has been hindered by insufficient molecular-level transport insights. We conducted molecular dynamics simulations to unravel the transport mechanism of solvent (water and alcohol) molecules in polymer membranes. For membranes with different hydrophobicity, alcohol concentrations at both solution-membrane and vapor–liquid interfaces were similar and approximated the activity in aqueous solution. We developed a thermodynamic cycle method for calculating interaction parameters and applied Flory-Huggins theory to quantify the solubility of solvent molecules. In dilute alcohol solutions (≤5 wt%), low solubility promotes molecular-level dispersion of solvent molecules in membranes, making diffusion coefficients nearly solubility independent. Based on these molecular-level insights, the factors affecting the separation factor/relative volatility of PV/distillation processes were quantified using proposed coefficients. These coefficients provide an intuitive understanding of why the separation factor of various polymer membranes is higher or lower than the relative volatility.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"127 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147380638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bayesian estimation enables uncertainty quantification, but analytical implementation is often intractable. As an approximate approach, the Markov Chain Monte Carlo (MCMC) method is widely used, though it entails a high computational cost due to frequent evaluations of the likelihood function. As an alternative approach, the sequential Monte Carlo (SMC) method is well known for time-series data, while its advantages for non-time series data using likelihood tempering have not been fully explored. In this study, we implemented an SMC algorithm with likelihood tempering and compared it with MCMC through two types of problems: toy problems and parameter uncertainty quantification problems for a methanation reactor model using real experimental data. In addition, we evaluated the effect of parallelization on SMC performance. The results showed that SMC with likelihood tempering exhibits substantially better computational efficiency and stability for problems with strong parameter correlations and with likelihood evaluations that require computationally expensive simulations.
{"title":"Sequential Monte Carlo with likelihood tempering and parallel implementation for uncertainty quantification","authors":"Tatsuki Maruchi, Tomoyuki Yajima, Yoshiaki Kawajiri","doi":"10.1002/aic.70319","DOIUrl":"https://doi.org/10.1002/aic.70319","url":null,"abstract":"Bayesian estimation enables uncertainty quantification, but analytical implementation is often intractable. As an approximate approach, the Markov Chain Monte Carlo (MCMC) method is widely used, though it entails a high computational cost due to frequent evaluations of the likelihood function. As an alternative approach, the sequential Monte Carlo (SMC) method is well known for time-series data, while its advantages for non-time series data using likelihood tempering have not been fully explored. In this study, we implemented an SMC algorithm with likelihood tempering and compared it with MCMC through two types of problems: toy problems and parameter uncertainty quantification problems for a methanation reactor model using real experimental data. In addition, we evaluated the effect of parallelization on SMC performance. The results showed that SMC with likelihood tempering exhibits substantially better computational efficiency and stability for problems with strong parameter correlations and with likelihood evaluations that require computationally expensive simulations.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"20 4 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147380987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Transition metal oxides, known for excellent redox properties, are widely used in exhaust purification. Doping is a common strategy to enhance redox performance. However, increased oxygen vacancy concentration also promotes water vapor adsorption, leading to a trade‐off between catalytic activity and hydrothermal stability. In this study, a strategy using Ce 0.5 Ni 0.1 Mg 0.1 Fe 0.1 Zn 0.1 Co 0.1 Ox high‐entropy hollow spheres (HEOs‐HS) to overcome the trade‐off between redox activity and hydrothermal stability in transition metal oxide. Synthesized via a glucose‐templated hydrothermal method, the HEOs‐HS catalyst demonstrated exceptional CO oxidation activity in the presence of 4.2 vol% moisture (160 h), and the catalyst exhibited low activation energy (27.84 kJ/mol). Comprehensive characterization revealed that HEOs‐HS possessed a higher concentration of oxygen vacancies; its unique hollow sphere architecture effectively mitigated excessive water adsorption. This protective morphology shielded active sites from direct water interaction. Thus, the synergistic integration of high‐entropy composition and hollow nanostructure successfully inhibited water poisoning, breaking the conventional activity‐stability trade‐off in humid environments.
过渡金属氧化物以其优异的氧化还原性能被广泛应用于废气净化。掺杂是提高氧化还原性能的常用策略。然而，氧空位浓度的增加也会促进水蒸气的吸附，导致催化活性和水热稳定性之间的权衡。在本研究中，采用Ce 0.5 Ni 0.1 Mg 0.1 Fe 0.1 Zn 0.1 Co 0.1 Ox高熵空心球（HEOs - HS）来克服过渡金属氧化物中氧化还原活性和水热稳定性之间的权衡。通过葡萄糖模板水热法合成的HEOs - HS催化剂在4.2 vol%的水分条件下（160 h）表现出优异的CO氧化活性，催化剂的活化能较低（27.84 kJ/mol）。综合表征表明，HEOs‐HS具有较高的氧空位浓度；其独特的中空球体结构有效地减轻了过量的水吸附。这种保护性形态保护活性位点不受水的直接作用。因此，高熵成分和中空纳米结构的协同集成成功地抑制了水中毒，打破了在潮湿环境中传统的活性-稳定性权衡。
{"title":"Engineering high‐entropy oxide hollow spheres to overcome the hydrothermal stability trade‐off in CO oxidation","authors":"Meiyu Shi, Wenli Gao, Yuan Shu, Kaixing Ru, Qiang Niu, Pengfei Zhang","doi":"10.1002/aic.70328","DOIUrl":"https://doi.org/10.1002/aic.70328","url":null,"abstract":"Transition metal oxides, known for excellent redox properties, are widely used in exhaust purification. Doping is a common strategy to enhance redox performance. However, increased oxygen vacancy concentration also promotes water vapor adsorption, leading to a trade‐off between catalytic activity and hydrothermal stability. In this study, a strategy using Ce <jats:sub>0.5</jats:sub> Ni <jats:sub>0.1</jats:sub> Mg <jats:sub>0.1</jats:sub> Fe <jats:sub>0.1</jats:sub> Zn <jats:sub>0.1</jats:sub> Co <jats:sub>0.1</jats:sub> Ox high‐entropy hollow spheres (HEOs‐HS) to overcome the trade‐off between redox activity and hydrothermal stability in transition metal oxide. Synthesized via a glucose‐templated hydrothermal method, the HEOs‐HS catalyst demonstrated exceptional CO oxidation activity in the presence of 4.2 vol% moisture (160 h), and the catalyst exhibited low activation energy (27.84 kJ/mol). Comprehensive characterization revealed that HEOs‐HS possessed a higher concentration of oxygen vacancies; its unique hollow sphere architecture effectively mitigated excessive water adsorption. This protective morphology shielded active sites from direct water interaction. Thus, the synergistic integration of high‐entropy composition and hollow nanostructure successfully inhibited water poisoning, breaking the conventional activity‐stability trade‐off in humid environments.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"52 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147373926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Renewable electricity-driven CO2 electrolysis offers a promising pathway toward achieving carbon neutrality. The electrochemical conversion of CO2-to-formate, particularly using metal oxide, has garnered significant attention. However, their ordered crystal structure limits catalytic activity and selectivity due to restricted active sites and suboptimal electronic properties. Herein, we for the first time present a novel approach by synthesizing co-amorphous zinc-indium oxide catalysts that capitalize on their disordered structure and abundant unsaturated sites. Experimental and theoretical investigations show that the Zn introduction promotes the formation of Lewis acid–base sites, and the induced charge redistribution modulates electron densities, thereby stabilizing OCHO* intermediates. The Zn1In1Ox catalyst with the highest disorder achieves nearly 100% formate Faradaic efficiency, with a high current density of 550 mA cm−2 and excellent stability. This work demonstrates the potential of co-amorphous structures and precise electronic tuning through synergistically efficient Lewis acid–base pairs to significantly enhance electrocatalytic performance for industrial CO2 reduction.
可再生电力驱动的二氧化碳电解为实现碳中和提供了一条有希望的途径。二氧化碳到甲酸的电化学转化，特别是使用金属氧化物，已经引起了极大的关注。然而，由于活性位点受限和电子性质欠佳，它们的有序晶体结构限制了催化活性和选择性。在此，我们首次提出了一种新方法，通过合成共无定形锌-铟氧化物催化剂，利用其无序结构和丰富的不饱和位点。实验和理论研究表明，Zn的引入促进了Lewis酸碱位的形成，诱导电荷重分布调节了电子密度，从而稳定了OCHO*中间体。无序度最高的Zn1In1Ox催化剂具有接近100%的甲酸法拉第效率，具有550 mA cm−2的高电流密度和优异的稳定性。这项工作表明，通过协同高效的刘易斯酸碱对，共无定形结构和精确的电子调谐具有显著提高工业二氧化碳还原电催化性能的潜力。
{"title":"Zn-induced active Lewis acid–base pairs in co-amorphous indium oxides enable industrial-level CO2-to-formate conversion","authors":"Dun Han, Akhmat Fauzi, Zhihui Liu, Yaxin Jin, Hai Liu, Yunsong Rao, Jianlong Lin, Yihan Xu, Wei Liu, Liang Wang, Sheng Zhang","doi":"10.1002/aic.70331","DOIUrl":"https://doi.org/10.1002/aic.70331","url":null,"abstract":"Renewable electricity-driven CO<sub>2</sub> electrolysis offers a promising pathway toward achieving carbon neutrality. The electrochemical conversion of CO<sub>2</sub>-to-formate, particularly using metal oxide, has garnered significant attention. However, their ordered crystal structure limits catalytic activity and selectivity due to restricted active sites and suboptimal electronic properties. Herein, we for the first time present a novel approach by synthesizing co-amorphous zinc-indium oxide catalysts that capitalize on their disordered structure and abundant unsaturated sites. Experimental and theoretical investigations show that the Zn introduction promotes the formation of Lewis acid–base sites, and the induced charge redistribution modulates electron densities, thereby stabilizing OCHO* intermediates. The Zn<sub>1</sub>In<sub>1</sub>O<sub><i>x</i></sub> catalyst with the highest disorder achieves nearly 100% formate Faradaic efficiency, with a high current density of 550 mA cm<sup>−2</sup> and excellent stability. This work demonstrates the potential of co-amorphous structures and precise electronic tuning through synergistically efficient Lewis acid–base pairs to significantly enhance electrocatalytic performance for industrial CO<sub>2</sub> reduction.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"11 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ke‐Xin Li, Weimin Huang, Qingyao Li, Hao Yuan, Shanshan Chen, Yuanhao Wang, Ralph T. Yang, Zhun Hu
Methane selective oxidation was regarded as the “Holy Grail” reaction in C 1 chemistry but remained limited by low yield and selectivity. Here, we reported an indium‐iron bimetallic catalyst (In x Fe y ) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH 4 activation, ·OOH coupled with ·CH 3 to form CH 3 OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe 3+ incorporation increased surface electron density and Fe 3+ centers, enhancing light absorption, charge separation, and ·CH 3 /·OOH generation. Excessive Fe 3+ shifted the HOMO positively and favored ·OH formation. In 0.6 Fe 0.4 achieved an optimal balance between ·CH 3 /·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g −1 ·h −1 , 94.3%). This work highlighted reactive species regulation and band‐structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.
甲烷选择性氧化反应被认为是c1化学中的“圣杯”反应，但由于收率低、选择性差而受到限制。在这里，我们报道了一种铟铁双金属催化剂（In x Fe y），它具有可调的In/Fe比，可以有效地将甲烷氧化成甲醇。猝灭实验表明，光生空穴导致了ch4活化，·OOH与·ch3偶联形成了ch3 OH，而·OH引起了过氧化。光电测试表明，Fe 3+的掺入增加了表面电子密度和Fe 3+中心，增强了光吸收、电荷分离和·CH 3 /·OOH的生成。过量的fe3 +使HOMO正向移位，有利于形成·OH。在0.6 μmol·g−1·h−1时，fe0.4在生成·CH 3 /·OOH和抑制·OH之间达到最佳平衡，收率和选择性最高（52.2 μmol·g−1·h−1,94.3%）。这项工作突出了反应物质调控和能带结构设计，为未来设计甲烷选择性氧化光热催化剂提供了指导。
{"title":"Bimetallic MIL ‐68 for methane selective oxidation: Trade‐off photon utilization and radical generation","authors":"Ke‐Xin Li, Weimin Huang, Qingyao Li, Hao Yuan, Shanshan Chen, Yuanhao Wang, Ralph T. Yang, Zhun Hu","doi":"10.1002/aic.70312","DOIUrl":"https://doi.org/10.1002/aic.70312","url":null,"abstract":"Methane selective oxidation was regarded as the “Holy Grail” reaction in C <jats:sub>1</jats:sub> chemistry but remained limited by low yield and selectivity. Here, we reported an indium‐iron bimetallic catalyst (In <jats:sub> <jats:italic>x</jats:italic> </jats:sub> Fe <jats:sub> <jats:italic>y</jats:italic> </jats:sub> ) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH <jats:sub>4</jats:sub> activation, ·OOH coupled with ·CH <jats:sub>3</jats:sub> to form CH <jats:sub>3</jats:sub> OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe <jats:sup>3+</jats:sup> incorporation increased surface electron density and Fe <jats:sup>3+</jats:sup> centers, enhancing light absorption, charge separation, and ·CH <jats:sub>3</jats:sub> /·OOH generation. Excessive Fe <jats:sup>3+</jats:sup> shifted the HOMO positively and favored ·OH formation. In <jats:sub>0.6</jats:sub> Fe <jats:sub>0.4</jats:sub> achieved an optimal balance between ·CH <jats:sub>3</jats:sub> /·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g <jats:sup>−1</jats:sup> ·h <jats:sup>−1</jats:sup> , 94.3%). This work highlighted reactive species regulation and band‐structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"15 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147373977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Meisi Chen, Yin Tong, Zekai Jin, Yajing Zhuang, Muhua Chen, Xinbao Zhu, Bo Fu
This study presents a novel biphasic absorbent (DDHI) regulated by a dual‐site ionic liquid to resolve the persistent trade‐off between absorption efficiency and regeneration energy in CO 2 capture. The high performance of DDHI is attributed to a newly verified acid–base dual sites synergistic mechanism. The basic site of [N 1111 ][Glu] synergizes with the primary amine (DETA) to enhance CO 2 capture, while its acidic site provides protons to promote product decomposition, significantly lowering the regeneration energy. This dual functionality results in a high CO 2 absorption capacity of 4.6 mol/kg (a 1.3‐fold increase over the IL‐free system) and a low regeneration energy of 1.71 GJ/t CO 2 , with excellent stability over multiple cycles under mild conditions. Spectroscopic analyses and quantum calculations confirm this mechanism, elucidating the distinct roles of the dual sites. This study provides a new perspective for the development of high efficiency, low energy biphasic absorbents.
本研究提出了一种新的双相吸收剂（DDHI），由双位离子液体调节，以解决二氧化碳捕获中吸收效率和再生能量之间的持续权衡。DDHI的高性能归因于新验证的酸碱双位点协同机制。[n1111][Glu]的碱性位点与伯胺（DETA）协同作用增强co2捕获，而其酸性位点提供质子促进产物分解，显著降低再生能量。这种双重功能导致高CO 2吸收能力为4.6 mol/kg（比无IL系统增加1.3倍）和低再生能量为1.71 GJ/t CO 2，在温和条件下多次循环具有出色的稳定性。光谱分析和量子计算证实了这一机制，阐明了双位点的独特作用。本研究为高效、低能双相吸收剂的开发提供了新的思路。
{"title":"High capacity CO 2 absorption and low energy regeneration in a biphasic absorbent driven by acid–base dual site synergy","authors":"Meisi Chen, Yin Tong, Zekai Jin, Yajing Zhuang, Muhua Chen, Xinbao Zhu, Bo Fu","doi":"10.1002/aic.70324","DOIUrl":"https://doi.org/10.1002/aic.70324","url":null,"abstract":"This study presents a novel biphasic absorbent (DDHI) regulated by a dual‐site ionic liquid to resolve the persistent trade‐off between absorption efficiency and regeneration energy in CO <jats:sub>2</jats:sub> capture. The high performance of DDHI is attributed to a newly verified acid–base dual sites synergistic mechanism. The basic site of [N <jats:sub>1111</jats:sub> ][Glu] synergizes with the primary amine (DETA) to enhance CO <jats:sub>2</jats:sub> capture, while its acidic site provides protons to promote product decomposition, significantly lowering the regeneration energy. This dual functionality results in a high CO <jats:sub>2</jats:sub> absorption capacity of 4.6 mol/kg (a 1.3‐fold increase over the IL‐free system) and a low regeneration energy of 1.71 GJ/t CO <jats:sub>2</jats:sub> , with excellent stability over multiple cycles under mild conditions. Spectroscopic analyses and quantum calculations confirm this mechanism, elucidating the distinct roles of the dual sites. This study provides a new perspective for the development of high efficiency, low energy biphasic absorbents.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"16 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147373976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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