CC bond cleavage in alkynes provides a powerful strategy for the functional group transformation of alkyne compounds, but it is challenging to balance reactivity and selectivity due to its high bond dissociation energy and inherently complex reaction pathways. In this work, we report the use of commercially available nitrates in acetonitrile for the mild aerobic oxidative cleavage of the alkyne CC bonds, resulting in the formation of carboxylic acids with good to excellent yields. This approach demonstrates broad functional group tolerance, applicable to those unactivated alkynes and substrates containing oxidation-sensitive groups. Mechanistic studies using EPR, FT-IR, and NMR measurements reveal that the excellent catalytic property arises from the formation of coordination intermediates between the alkyne and zinc nitrate, stabilized by acetonitrile through ion–dipole interactions. This stabilization promotes alkyne activation, facilitates the oxygen atom transfer (OAT) from nitrate to the CC bond and reduces the nitrate to nitrogen oxides, which then act as free-radical initiators to trigger a chain reaction and accelerate the oxidative cleavage of the CC bond, with molecular oxygen serving as the terminal oxidant.
{"title":"Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions","authors":"Chao Xie, Zejun Liu, Huichao Wang, Qidong Hou, Hengli Qian, Zhiwei Jiang, Meiting Ju","doi":"10.1016/j.jcat.2026.116719","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116719","url":null,"abstract":"C<ce:glyph name=\"tbnd\"></ce:glyph>C bond cleavage in alkynes provides a powerful strategy for the functional group transformation of alkyne compounds, but it is challenging to balance reactivity and selectivity due to its high bond dissociation energy and inherently complex reaction pathways. In this work, we report the use of commercially available nitrates in acetonitrile for the mild aerobic oxidative cleavage of the alkyne C<ce:glyph name=\"tbnd\"></ce:glyph>C bonds, resulting in the formation of carboxylic acids with good to excellent yields. This approach demonstrates broad functional group tolerance, applicable to those unactivated alkynes and substrates containing oxidation-sensitive groups. Mechanistic studies using EPR, FT-IR, and NMR measurements reveal that the excellent catalytic property arises from the formation of coordination intermediates between the alkyne and zinc nitrate, stabilized by acetonitrile through ion–dipole interactions. This stabilization promotes alkyne activation, facilitates the oxygen atom transfer (OAT) from nitrate to the C<ce:glyph name=\"tbnd\"></ce:glyph>C bond and reduces the nitrate to nitrogen oxides, which then act as free-radical initiators to trigger a chain reaction and accelerate the oxidative cleavage of the C<ce:glyph name=\"tbnd\"></ce:glyph>C bond, with molecular oxygen serving as the terminal oxidant.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"73 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.jcat.2026.116713
Meng Xu , Zhongliang Tang , Yue Wu , Menglin Xie , Biao Meng , Xiao Chi , Xiaojiang Yu , Xiaoling Liu , Shibo Xi , Yu Zhou , Jun Wang
Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive- and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework via an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving > 92% yield and a turnover frequency (TOF) of 466 h−1 without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. In situ spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.
{"title":"BEA zeolite encapsulated defective Co sites for solvent- and additive-free N-alkylation of amines with aromatic alcohols","authors":"Meng Xu , Zhongliang Tang , Yue Wu , Menglin Xie , Biao Meng , Xiao Chi , Xiaojiang Yu , Xiaoling Liu , Shibo Xi , Yu Zhou , Jun Wang","doi":"10.1016/j.jcat.2026.116713","DOIUrl":"10.1016/j.jcat.2026.116713","url":null,"abstract":"<div><div>Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive- and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework <em>via</em> an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving > 92% yield and a turnover frequency (TOF) of 466 h<sup>−1</sup> without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. <em>In situ</em> spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116713"},"PeriodicalIF":6.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.jcat.2026.116711
Xiaoyu Nie , Chengyi Ou , Jingwen Liang , Chenglong Ru , Xiaobo Pan , Sibo Wang , Zhi-An Lan
The separation and transport efficiency of photogenerated charge carriers are critical factors determining the photocatalytic performance of semiconductors. However, the lack of a direct and effective driving force for charge separation leads to rapid recombination of most photogenerated carriers within the bulk or on the surface of photocatalysts, severely limiting their output efficiency. Constructing an internal polarization electric field to drive the directional migration of charges and suppress carrier recombination has been demonstrated as an effective strategy. In this study, we designed and synthesized two conjugated polymers with distinct symmetries via a local π-skeleton modulation strategy of molecular units. We systematically clarified the regulatory mechanism underlying the disruption of molecular structural unit symmetry on the photocatalytic charge transport process. Both experimental results and theoretical calculations demonstrated that the breaking of molecular unit symmetry induces an internal electric field within the photocatalyst, which provides an intrinsic driving force for the directional migration and rapid accumulation of electrons. This process establishes a continuous π-electron delocalization channel, creating a “charge superhighway”, while reducing the exciton binding energy (Eb) to significantly suppress carrier recombination, thereby substantially enhancing the photocatalytic performance. This study demonstrates the polarization effect caused by the disruption of molecular unit symmetry, which can amplify the electric field strength to optimize charge separation and provide a design option for high-efficiency organic photocatalysts.
{"title":"Inducing polar electric fields via molecular unit symmetry breaking for boosting photocatalysis","authors":"Xiaoyu Nie , Chengyi Ou , Jingwen Liang , Chenglong Ru , Xiaobo Pan , Sibo Wang , Zhi-An Lan","doi":"10.1016/j.jcat.2026.116711","DOIUrl":"10.1016/j.jcat.2026.116711","url":null,"abstract":"<div><div>The separation and transport efficiency of photogenerated charge carriers are critical factors determining the photocatalytic performance of semiconductors. However, the lack of a direct and effective driving force for charge separation leads to rapid recombination of most photogenerated carriers within the bulk or on the surface of photocatalysts, severely limiting their output efficiency. Constructing an internal polarization electric field to drive the directional migration of charges and suppress carrier recombination has been demonstrated as an effective strategy. In this study, we designed and synthesized two conjugated polymers with distinct symmetries via a local π-skeleton modulation strategy of molecular units. We systematically clarified the regulatory mechanism underlying the disruption of molecular structural unit symmetry on the photocatalytic charge transport process. Both experimental results and theoretical calculations demonstrated that the breaking of molecular unit symmetry induces an internal electric field within the photocatalyst, which provides an intrinsic driving force for the directional migration and rapid accumulation of electrons. This process establishes a continuous π-electron delocalization channel, creating a “charge superhighway”, while reducing the exciton binding energy (<em>E</em><sub>b</sub>) to significantly suppress carrier recombination, thereby substantially enhancing the photocatalytic performance. This study demonstrates the polarization effect caused by the disruption of molecular unit symmetry, which can amplify the electric field strength to optimize charge separation and provide a design option for high-efficiency organic photocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116711"},"PeriodicalIF":6.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.jcat.2026.116712
Chunling Zhang, Shuangshuang Yu, Shujie Shen, Huimin Dan, Wei Wu, Jieyuan Li, Fan Dong
The treatment of nitrate (NO3−) pollutants is of critical importance for both human health and sustainable environmental development. The efficient conversion of low-concentration NO3− is mainly challenged by the competing hydrogen evolution side reactions and the lack of efficient hydrogen sources for deep hydrogenation. Here, we report a redox-enhanced photocatalytic system by constructing spatially separated CuxO nanoclusters (CuxO NCs) and oxygen vacancies (OVs) as dual active sites on a TiO2 nanotube support. CuxO NCs, as electron enrichment centers, significantly enhance the adsorption and activation capabilities for NO3−, thereby enabling NO3− to be activated into the key intermediate nitrite (NO2−). OVs, as efficient hole-trapping sites, accelerate the oxidation half-reaction, promoting the generation of highly reactive hydrogen radicals (H). Most importantly, the directional addition of the H to NO2− facilitates its deep reduction via a H-mediated pathway, leading to the highly selective generation of ammonia (NH3). Almost 100 % of the NO3− conversion ratio and a competitive NH3 selectivity (98.3 ± 0.16 %) are achieved in this system. This study highlights the critical roles of NO3− activation and H in efficient NO3− conversion, providing an innovative strategy for the resource utilization of NO3−-contaminated wastewater.
Environmental Implication: A redox-enhanced photocatalytic system is constructed to enable efficient activation of NO3− to NO2− and subsequently H-mediated hydrogenation. As a result, nearly complete NO3− removal ratio (∼100 %) with high selectivity toward NH3 (98.3 ± 0.16 %) is achieved. This study provides insights and guidance for the efficient conversion and resource utilization of low-concentration NO3−, significantly advancing the application of photocatalytic technology in environmental remediation and resource recovery. It also offers support for the establishment of a sustainable nitrogen cycle system.
{"title":"Deep hydrogenation of nitrite intermediate with H-radicals for promoted nitrate reduction to ammonia","authors":"Chunling Zhang, Shuangshuang Yu, Shujie Shen, Huimin Dan, Wei Wu, Jieyuan Li, Fan Dong","doi":"10.1016/j.jcat.2026.116712","DOIUrl":"10.1016/j.jcat.2026.116712","url":null,"abstract":"<div><div>The treatment of nitrate (NO<sub>3</sub><sup>−</sup>) pollutants is of critical importance for both human health and sustainable environmental development. The efficient conversion of low-concentration NO<sub>3</sub><sup>−</sup> is mainly challenged by the competing hydrogen evolution side reactions and the lack of efficient hydrogen sources for deep hydrogenation. Here, we report a redox-enhanced photocatalytic system by constructing spatially separated Cu<sub>x</sub>O nanoclusters (Cu<sub>x</sub>O NCs) and oxygen vacancies (OVs) as dual active sites on a TiO<sub>2</sub> nanotube support. Cu<sub>x</sub>O NCs, as electron enrichment centers, significantly enhance the adsorption and activation capabilities for NO<sub>3</sub><sup>−</sup>, thereby enabling NO<sub>3</sub><sup>−</sup> to be activated into the key intermediate nitrite (NO<sub>2</sub><sup>−</sup>). OVs, as efficient hole-trapping sites, accelerate the oxidation half-reaction, promoting the generation of highly reactive hydrogen radicals (<sup><img></sup>H). Most importantly, the directional addition of the <sup><img></sup>H to NO<sub>2</sub><sup>−</sup> facilitates its deep reduction <em>via</em> a <sup><img></sup>H-mediated pathway, leading to the highly selective generation of ammonia (NH<sub>3</sub>). Almost 100 % of the NO<sub>3</sub><sup>−</sup> conversion ratio and a competitive NH<sub>3</sub> selectivity (98.3 ± 0.16 %) are achieved in this system. This study highlights the critical roles of NO<sub>3</sub><sup>−</sup> activation and <sup><img></sup>H in efficient NO<sub>3</sub><sup>−</sup> conversion, providing an innovative strategy for the resource utilization of NO<sub>3</sub><sup>−</sup>-contaminated wastewater.</div><div><strong>Environmental Implication:</strong> A redox-enhanced photocatalytic system is constructed to enable efficient activation of NO<sub>3</sub><sup>−</sup> to NO<sub>2</sub><sup>−</sup> and subsequently <sup><img></sup>H-mediated hydrogenation. As a result, nearly complete NO<sub>3</sub><sup>−</sup> removal ratio (∼100 %) with high selectivity toward NH<sub>3</sub> (98.3 ± 0.16 %) is achieved. This study provides insights and guidance for the efficient conversion and resource utilization of low-concentration NO<sub>3</sub><sup>−</sup>, significantly advancing the application of photocatalytic technology in environmental remediation and resource recovery. It also offers support for the establishment of a sustainable nitrogen cycle system.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116712"},"PeriodicalIF":6.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.jcat.2026.116704
Qiangwei Li , Ting Yang , Xiao-Feng Wu
Owing to the high reactivity of the carbon–carbon triple bond, alkynes can react with various reagents to give functionalized alkenes and alkanes, making it a useful compound to build complex molecules. Herein, we reported a one-pot, two-step strategy which use arenes and alkynes as the reactant combined with carbon monoxide to afford α, β-unsaturated esters. The transformation goes through iodonium ions intermediate and proceed under mild conditions, a series of the target products were generated in good to excellent yields.
{"title":"A four-component carbonylation reaction of terminal alkynes and arenes toward α, β-unsaturated esters","authors":"Qiangwei Li , Ting Yang , Xiao-Feng Wu","doi":"10.1016/j.jcat.2026.116704","DOIUrl":"10.1016/j.jcat.2026.116704","url":null,"abstract":"<div><div>Owing to the high reactivity of the carbon–carbon triple bond, alkynes can react with various reagents to give functionalized alkenes and alkanes, making it a useful compound to build complex molecules. Herein, we reported a one-pot, two-step strategy which use arenes and alkynes as the reactant combined with carbon monoxide to afford α, β-unsaturated esters. The transformation goes through iodonium ions intermediate and proceed under mild conditions, a series of the target products were generated in good to excellent yields.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116704"},"PeriodicalIF":6.5,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.jcat.2026.116714
Jingjing Yang , Ting Li , Chengyan Zou , Jinlan Cheng , Kaiyi Su , Bo Jiang , Hao Li , Zhengwei Li , Chaofeng Zhang
Compared with the aromatic monomer preparation, the lignin catalytic transformation to dimers with higher added value has received extensive attention recently. Different from the stepwise tandem synthesis strategies for dimer preparation, which involve the first lignin depolymerization to monomers and following monomer coupling to dimers, we here achieved the in-situ photocatalytic reductive fragmentation-coupling of the pre-oxidized lignin β-O-4 linkages to pinacols. The optimized TiO2-R(1 1 0) (rutile) could efficiently achieve the transformation of 2-phenoxy-1-phenylethanone with i-PrOH as the hydrogen donor under UV LED irradiation, providing an 83.0% yield of 2,3-diphenylbutane-2,3-diol and a 78% yield of phenol in 15 h. Mechanism studies indicated that the activated TiO2-R with critical surface Ti3+ species under UV LED irradiation mediated the first photocatalytic cleavage of the Cβ–OAr bond of 2-phenoxy-1-phenylethanone to phenol and acetophenone. The generated acetophenone further underwent semi-reduction and carbon radical coupling to provide the pinacol, dominated by the UV LED irradiation and improved by the TiO2-R(1 1 0) surface. The revelation of the catalytic mechanism can provide ideas for the subsequent direct conversion of lignin to high-value dimer products.
{"title":"Photocatalytic in-situ reductive fragmentation and coupling of lignin β-O-4 linkages to pinacols","authors":"Jingjing Yang , Ting Li , Chengyan Zou , Jinlan Cheng , Kaiyi Su , Bo Jiang , Hao Li , Zhengwei Li , Chaofeng Zhang","doi":"10.1016/j.jcat.2026.116714","DOIUrl":"10.1016/j.jcat.2026.116714","url":null,"abstract":"<div><div>Compared with the aromatic monomer preparation, the lignin catalytic transformation to dimers with higher added value has received extensive attention recently. Different from the stepwise tandem synthesis strategies for dimer preparation, which involve the first lignin depolymerization to monomers and following monomer coupling to dimers, we here achieved the <em>in-situ</em> photocatalytic reductive fragmentation-coupling of the pre-oxidized lignin β-O-4 linkages to pinacols. The optimized TiO<sub>2</sub>-R(1 1 0) (rutile) could efficiently achieve the transformation of 2-phenoxy-1-phenylethanone with <em>i</em>-PrOH as the hydrogen donor under UV LED irradiation, providing an 83.0% yield of 2,3-diphenylbutane-2,3-diol and a 78% yield of phenol in 15 h. Mechanism studies indicated that the activated TiO<sub>2</sub>-R with critical surface Ti<sup>3+</sup> species under UV LED irradiation mediated the first photocatalytic cleavage of the C<sub>β</sub>–OAr bond of 2-phenoxy-1-phenylethanone to phenol and acetophenone. The generated acetophenone further underwent semi-reduction and carbon radical coupling to provide the pinacol, dominated by the UV LED irradiation and improved by the TiO<sub>2</sub>-R(1 1 0) surface. The revelation of the catalytic mechanism can provide ideas for the subsequent direct conversion of lignin to high-value dimer products.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116714"},"PeriodicalIF":6.5,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.jcat.2026.116706
Jinchuan Zhang , Yunpeng Zou , Shuai Chen , Yang Zhao , Di Jin , Jialin Chen , Jijie Li , Yuewen Mu , Wen-Yan Zan , Fengwei Zhang
Aiming at the critical challenges of competitive hydrogen evolution reaction (HER) and sluggish reaction kinetics in CO2 electroreduction reaction (CO2RR), a uniquely structured nitrogen-doped porous carbon-embedded Ni single-atom catalyst (Ni-N3O2/NPC) was designed and synthesized by virtue of density functional theory (DFT) calculations and mild thermal treatment strategies. The as-synthesized catalyst was verified by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption spectroscopy (XAS) to possess an asymmetric configuration featuring Ni-N3O1 motif with axial oxygen ligand, which agrees well with the DFT modeling. CO2RR results validated that the Ni-N3O2/NPC-400 catalyst exhibited 99% Faraday efficiency for CO (FECO) across a wide potential window of −0.3 to −1.0 V vs. reversible hydrogen electrode (RHE) in flow cell, reaching a maximum FECO of 99.9% at −1.0 V vs. RHE with an turnover frequency (TOF) of 63,579 h−1, showcasing potential for industrial CO2 emission reduction. In situ attenuated total reflection infrared spectroscopy (ATR-IR) further confirmed the formation of key *COOH and *CO intermediates during the CO2RR process. Theoretical calculation unveiled that the axial oxygen ligand in Ni-N3O2 configuration synergistically promoted CO2RR kinetics by inducing electronic polarization. The present work not only provides a theoretical basis for axial ligand engineering to regulate the electronic state of single-atom catalysts, but also opens up a new direction for designing high-efficiency CO2RR catalysts.
{"title":"Axial coordination and asymmetric structure synergistically induce electron polarization at Ni sites to promote efficient CO2 electroreduction into CO","authors":"Jinchuan Zhang , Yunpeng Zou , Shuai Chen , Yang Zhao , Di Jin , Jialin Chen , Jijie Li , Yuewen Mu , Wen-Yan Zan , Fengwei Zhang","doi":"10.1016/j.jcat.2026.116706","DOIUrl":"10.1016/j.jcat.2026.116706","url":null,"abstract":"<div><div>Aiming at the critical challenges of competitive hydrogen evolution reaction (HER) and sluggish reaction kinetics in CO<sub>2</sub> electroreduction reaction (CO<sub>2</sub>RR), a uniquely structured nitrogen-doped porous carbon-embedded Ni single-atom catalyst (Ni-N<sub>3</sub>O<sub>2</sub>/NPC) was designed and synthesized by virtue of density functional theory (DFT) calculations and mild thermal treatment strategies. The as-synthesized catalyst was verified by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption spectroscopy (XAS) to possess an asymmetric configuration featuring Ni-N<sub>3</sub>O<sub>1</sub> motif with axial oxygen ligand, which agrees well with the DFT modeling. CO<sub>2</sub>RR results validated that the Ni-N<sub>3</sub>O<sub>2</sub>/NPC-400 catalyst exhibited 99% Faraday efficiency for CO (FE<sub>CO</sub>) across a wide potential window of −0.3 to −1.0 V <em>vs</em>. reversible hydrogen electrode (RHE) in flow cell, reaching a maximum FE<sub>CO</sub> of 99.9% at −1.0 V <em>vs</em>. RHE with an turnover frequency (TOF) of 63,579 h<sup>−1</sup>, showcasing potential for industrial CO<sub>2</sub> emission reduction. <em>In situ</em> attenuated total reflection infrared spectroscopy (ATR-IR) further confirmed the formation of key *COOH and *CO intermediates during the CO<sub>2</sub>RR process. Theoretical calculation unveiled that the axial oxygen ligand in Ni-N<sub>3</sub>O<sub>2</sub> configuration synergistically promoted CO<sub>2</sub>RR kinetics by inducing electronic polarization. The present work not only provides a theoretical basis for axial ligand engineering to regulate the electronic state of single-atom catalysts, but also opens up a new direction for designing high-efficiency CO<sub>2</sub>RR catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116706"},"PeriodicalIF":6.5,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.jcat.2026.116705
Martin Hedevang , Lars Mohrhusen , Filip Hallböök , Dorotea Gajdek , Lindsay R. Merte , Sara Blomberg , Jeppe V. Lauritsen
Hydrodeoxygenation (HDO) is a catalytic process applied for the reduction of oxygen levels in hydrocarbons from bio-derived feedstock as part of the processing into renewable fuel. The MoS2-based hydrotreating catalysts, currently being applied for the HDO reaction, are exposed to a complex environment consisting of O-rich hydrocarbons and water, which adversely impacts the state and stability of the catalyst. Here, we analyze the structural and chemical state changes of MoS2 in HDO-relevant conditions using a combination of surface-sensitive techniques applied to a planar model system consisting of supported and structurally well-defined single-layer MoS2 nanoparticles supported on Au(111). As observed by scanning tunnelling microscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), the exposure to mbar pressure of H2O at 600 K induces clear changes in both the shape and size of the MoS2 nanoparticles, explained by a preferential oxidation and etching of MoS2 edges. MoOx is observed on the surface due to the spatial separation of the oxide and etched sulfide phase. Interestingly, when H2/H2O gas mixtures are applied, the sulfur reduction and oxidation of MoS2 appear to be decoupled, indicating that the removal of edge S species is not a prerequisite for oxidation. Furthermore, the formed MoOx showed a preferred reduction of the oxide over the sulfide. Importantly, the atom-resolved imaging reveals that the progressive etching and phase segregation of MoS2 maintains access to pristine edge sites of the single-layer MoS2, explaining why HDO activity can be maintained even for highly oxidized catalysts.
{"title":"In-situ NAP-XPS reveals water-induced phase segregation of MoS2 nanoparticles in hydrodeoxygenation catalysis","authors":"Martin Hedevang , Lars Mohrhusen , Filip Hallböök , Dorotea Gajdek , Lindsay R. Merte , Sara Blomberg , Jeppe V. Lauritsen","doi":"10.1016/j.jcat.2026.116705","DOIUrl":"10.1016/j.jcat.2026.116705","url":null,"abstract":"<div><div>Hydrodeoxygenation (HDO) is a catalytic process applied for the reduction of oxygen levels in hydrocarbons from bio-derived feedstock as part of the processing into renewable fuel. The MoS<sub>2</sub>-based hydrotreating catalysts, currently being applied for the HDO reaction, are exposed to a complex environment consisting of O-rich hydrocarbons and water, which adversely impacts the state and stability of the catalyst. Here, we analyze the structural and chemical state changes of MoS<sub>2</sub> in HDO-relevant conditions using a combination of surface-sensitive techniques applied to a planar model system consisting of supported and structurally well-defined single-layer MoS<sub>2</sub> nanoparticles supported on Au(111). As observed by scanning tunnelling microscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), the exposure to mbar pressure of H<sub>2</sub>O at 600 K induces clear changes in both the shape and size of the MoS<sub>2</sub> nanoparticles, explained by a preferential oxidation and etching of MoS<sub>2</sub> edges. MoO<sub>x</sub> is observed on the surface due to the spatial separation of the oxide and etched sulfide phase. Interestingly, when H<sub>2</sub>/H<sub>2</sub>O gas mixtures are applied, the sulfur reduction and oxidation of MoS<sub>2</sub> appear to be decoupled, indicating that the removal of edge S species is not a prerequisite for oxidation. Furthermore, the formed MoO<sub>x</sub> showed a preferred reduction of the oxide over the sulfide. Importantly, the atom-resolved imaging reveals that the progressive etching and phase segregation of MoS<sub>2</sub> maintains access to pristine edge sites of the single-layer MoS<sub>2</sub>, explaining why HDO activity can be maintained even for highly oxidized catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116705"},"PeriodicalIF":6.5,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.jcat.2026.116709
Hiyab T. Mekonnen , Guanhua Wang , Sukaran Arora , Arjun Raghuraman , Linda Broadbelt , Justin M. Notestein
The isomerization of epoxides is a valuable transformation in synthetic chemistry, offering an atom-economical route to aldehydes and ketones from readily available substrates. In this study, we investigate tris(pentafluorophenyl)borane (B(C6F5)3 or BCF) as a Lewis acid catalyst for the Meinwald rearrangement using propylene oxide and other epoxides as models. The effects of residual water, temperature, and solvent properties such as coordination strength, polarity, and hydrogen-bonding ability are systematically examined to determine their impact on catalytic activity and product selectivity. 19F and 2D HOESY NMR spectroscopy, along with density functional theory (DFT) calculations, reveal key BCF–solvent interactions that govern catalytic behavior. In particular, [BCF·OH2]·(solvent) pre-catalyst complexes are proposed to explain the activation period observed in strongly coordinating solvents. BCF is very active for aldehyde formation, and these findings highlight the critical roles of water activity and solvent coordination strength in modulating catalytic activity by determining the amount of free BCF. In addition, hydrogen-bonding ability of the solvent governs the selectivity towards Meinwald rearrangement products in BCF-catalyzed reactions. The insights gained are broadly applicable to understanding catalyst–solvent interactions in other organoborane systems.
{"title":"Tris(pentafluorophenyl)borane (BCF)-catalyzed meinwald rearrangement of epoxides","authors":"Hiyab T. Mekonnen , Guanhua Wang , Sukaran Arora , Arjun Raghuraman , Linda Broadbelt , Justin M. Notestein","doi":"10.1016/j.jcat.2026.116709","DOIUrl":"10.1016/j.jcat.2026.116709","url":null,"abstract":"<div><div>The isomerization of epoxides is a valuable transformation in synthetic chemistry, offering an atom-economical route to aldehydes and ketones from readily available substrates. In this study, we investigate tris(pentafluorophenyl)borane (B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> or BCF) as a Lewis acid catalyst for the Meinwald rearrangement using propylene oxide and other epoxides as models. The effects of residual water, temperature, and solvent properties such as coordination strength, polarity, and hydrogen-bonding ability are systematically examined to determine their impact on catalytic activity and product selectivity. <sup>19</sup>F and 2D HOESY NMR spectroscopy, along with density functional theory (DFT) calculations, reveal key BCF–solvent interactions that govern catalytic behavior. In particular, [BCF·OH<sub>2</sub>]·(solvent) pre-catalyst complexes are proposed to explain the activation period observed in strongly coordinating solvents. BCF is very active for aldehyde formation, and these findings highlight the critical roles of water activity and solvent coordination strength in modulating catalytic activity by determining the amount of free BCF. In addition, hydrogen-bonding ability of the solvent governs the selectivity towards Meinwald rearrangement products in BCF-catalyzed reactions<em>.</em> The insights gained are broadly applicable to understanding catalyst–solvent interactions in other organoborane systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116709"},"PeriodicalIF":6.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.jcat.2026.116710
Xiao-Rong Wen , Shan-Shan Chen , Wen-Jun Xie , Hong-Ru Li , Liang-Nian He
Electrocatalytic carbon dioxide reduction (eCO2R) to ethylene (C2H4) offers a promising pathway toward carbon–neutral cycles and sustainable chemical synthesis. In eCO2R to C2H4, copper-based electrocatalysts, particularly Cu2O, have been widely used. Nevertheless, product selectivity to C2H4 is still quite limited due to the insufficient enrichment of key intermediates and slow C–C coupling kinetics. Herein, the double-shelled hollow mesoporous Cu2O was fabricated through the soft-templating method. And the cavity size and pore architecture of the resulting Cu2O catalysts could be precisely tailored by adjusting the alkyl chain length of the surfactant templates alkyltrimethylammonium bromides. When applied to eCO2R, the as-prepared Cu2O material with tetradecyltrimethylammonium bromide (TTAB) as template exhibited a remarkable Faradaic efficiency of 43.3 ± 0.8% for C2H4 at an industrial-level current density of 549.8 mA cm−2. Experimental and theoretical investigations reveal that its high activity and selectivity toward C2H4 stem from the suitable cavity configuration, which enriches key *CO intermediates and promotes their dimerization via a spatial confinement effect. This study provides valuable insights into the architectural design of efficient catalysts for CO2-to-C2H4 conversion.
电催化二氧化碳还原（eCO2R）制乙烯（C2H4）为实现碳中性循环和可持续化学合成提供了一条有前途的途径。在eCO2R到C2H4中，铜基电催化剂，特别是Cu2O已被广泛使用。然而，由于关键中间体富集不足和C-C耦合动力学缓慢，产物对C2H4的选择性仍然很有限。本文采用软模板法制备了双壳中空介孔Cu2O。通过调整表面活性剂模板烷基三甲基溴化铵的烷基链长度，可以精确地调整Cu2O催化剂的空腔大小和孔结构。以十四烷基三甲基溴化铵（TTAB）为模板制备的Cu2O材料在工业级电流密度549.8 mA cm−2下，对C2H4的法拉第效率为43.3±0.8%。实验和理论研究表明，其对C2H4的高活性和选择性源于合适的腔体结构，它通过空间约束效应富集了关键的*CO中间体并促进了它们的二聚化。该研究为CO2-to-C2H4转化的高效催化剂的结构设计提供了有价值的见解。
{"title":"Cavity-confined Cu2O nanoreactors for efficient CO2 electroreduction to ethylene","authors":"Xiao-Rong Wen , Shan-Shan Chen , Wen-Jun Xie , Hong-Ru Li , Liang-Nian He","doi":"10.1016/j.jcat.2026.116710","DOIUrl":"10.1016/j.jcat.2026.116710","url":null,"abstract":"<div><div>Electrocatalytic carbon dioxide reduction (eCO<sub>2</sub>R) to ethylene (C<sub>2</sub>H<sub>4</sub>) offers a promising pathway toward carbon–neutral cycles and sustainable chemical synthesis. In eCO<sub>2</sub>R to C<sub>2</sub>H<sub>4</sub>, copper-based electrocatalysts, particularly Cu<sub>2</sub>O, have been widely used. Nevertheless, product selectivity to C<sub>2</sub>H<sub>4</sub> is still quite limited due to the insufficient enrichment of key intermediates and slow C–C coupling kinetics. Herein, the double-shelled hollow mesoporous Cu<sub>2</sub>O was fabricated through the soft-templating method. And the cavity size and pore architecture of the resulting Cu<sub>2</sub>O catalysts could be precisely tailored by adjusting the alkyl chain length of the surfactant templates alkyltrimethylammonium bromides. When applied to eCO<sub>2</sub>R, the as-prepared Cu<sub>2</sub>O material with tetradecyltrimethylammonium bromide (TTAB) as template exhibited a remarkable Faradaic efficiency of 43.3 ± 0.8% for C<sub>2</sub>H<sub>4</sub> at an industrial-level current density of 549.8 mA cm<sup>−2</sup>. Experimental and theoretical investigations reveal that its high activity and selectivity toward C<sub>2</sub>H<sub>4</sub> stem from the suitable cavity configuration, which enriches key *CO intermediates and promotes their dimerization via a spatial confinement effect. This study provides valuable insights into the architectural design of efficient catalysts for CO<sub>2</sub>-to-C<sub>2</sub>H<sub>4</sub> conversion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116710"},"PeriodicalIF":6.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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