Pub Date : 2026-02-09DOI: 10.1021/acscatal.5c07192
Katarzyna Świrk Da Costa,Paulina Summa,Marco Fabbiani,Dumitrita Spinu,Valentin Valtchev,Ludovic Pinard,Magnus Ro̷nning
Nickel (Ni) phyllosilicate-derived catalysts have recently gained attention for the CO2 reforming of methane. However, understanding of the underlying reduction pathways and structural factors that determine stable catalytic performance is still missing. Herein, we developed a one-pot synthesis with ammonia solution to produce nickel catalysts supported on silica, utilizing a modified KIT-6 protocol. Under the proposed alkaline conditions (pH = 9), the silanol groups were deprotonated (Si–O–) and the resulting negatively charged oxide surface could interact with Ni2+. This approach facilitated the in situ formation of Ni phyllosilicate within the silica framework, which contained isolated surface hydroxyl groups. In situ XAS-XRD revealed the presence of thermally stable crystalline Ni phyllosilicate, Ni3Si2O5(OH)4, with time-resolved XANES providing complementary insight into the redox transformation of nickel species associated with dehydroxylation. Partially unreduced nickel species retained a cationic state during the catalytic reaction at 700 °C, with a higher amount of nickel phyllosilicate observed after 50 h in contrast to the state after 1 h. On the whole, the one-pot synthesis produced small Ni crystallites with improved dispersion, both of which had a part in ensuring stable catalytic performance. We also uncovered the crucial role of ionic species (Ni+ and Ni2+) limiting the carbon formation via CO disproportionation (2CO ⇌ C(s) + CO2) on the KIT-6-templated silica. This study provides valuable insights into the design of more stable methane reforming catalysts.
{"title":"In Situ Insights into Ni Phyllosilicate Evolution: Cationic Ni Species as Key to Enhanced Stability in Methane-Rich Dry Reforming","authors":"Katarzyna Świrk Da Costa,Paulina Summa,Marco Fabbiani,Dumitrita Spinu,Valentin Valtchev,Ludovic Pinard,Magnus Ro̷nning","doi":"10.1021/acscatal.5c07192","DOIUrl":"https://doi.org/10.1021/acscatal.5c07192","url":null,"abstract":"Nickel (Ni) phyllosilicate-derived catalysts have recently gained attention for the CO2 reforming of methane. However, understanding of the underlying reduction pathways and structural factors that determine stable catalytic performance is still missing. Herein, we developed a one-pot synthesis with ammonia solution to produce nickel catalysts supported on silica, utilizing a modified KIT-6 protocol. Under the proposed alkaline conditions (pH = 9), the silanol groups were deprotonated (Si–O–) and the resulting negatively charged oxide surface could interact with Ni2+. This approach facilitated the in situ formation of Ni phyllosilicate within the silica framework, which contained isolated surface hydroxyl groups. In situ XAS-XRD revealed the presence of thermally stable crystalline Ni phyllosilicate, Ni3Si2O5(OH)4, with time-resolved XANES providing complementary insight into the redox transformation of nickel species associated with dehydroxylation. Partially unreduced nickel species retained a cationic state during the catalytic reaction at 700 °C, with a higher amount of nickel phyllosilicate observed after 50 h in contrast to the state after 1 h. On the whole, the one-pot synthesis produced small Ni crystallites with improved dispersion, both of which had a part in ensuring stable catalytic performance. We also uncovered the crucial role of ionic species (Ni+ and Ni2+) limiting the carbon formation via CO disproportionation (2CO ⇌ C(s) + CO2) on the KIT-6-templated silica. This study provides valuable insights into the design of more stable methane reforming catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138516","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}
Low-valence copper species (Cuδ+, 0 < δ < 1) on Cu-based electrocatalysts are crucial for C–C coupling to form C2+ products, yet the stability of Cuδ+ especially at industrial-scale current, remains a significant challenge. Herein, we designed a strongly correlated metal–metal oxide nanosphere catalyst (Cu@CeO2–x) that stabilizes Cuδ+ species and establishes a Cu0–Cu+ interface to better regulate hydrogen adsorption, achieving a maximum faradaic efficiency for C2+ products of 82.5% at 300 mA cm–2 and −0.62 VRHE, while maintaining stable CO2 reduction reaction performance for over 72 h. Operando X-ray absorption fine structure and in-situ Raman spectroscopy indicated that Cu@CeO2–x underwent in-situ surface reconstruction, enabling a CeO2-mediated Cuδ+ redox cycle. This dynamic charge equilibrium forms a Cu0–Cu+ interface through the self-sacrifice of Ce sites to avoid an immoderate reduction of Cu. Furthermore, density functional calculations together with in-situ attenuated total reflection–surface-enhanced infrared absorption spectroscopy indicated that Cu0–Cu+ interface enhances *CO adsorption, and facilitates C–C coupling for C2+ products formation. The findings provide a blueprint for designing Cu-based electrocatalysts to combat rapid deactivation, enhancing performance toward higher-value products.
{"title":"Dynamic Evolution of Cuδ+ Quantification in Mutually Reinforced Copper–Ceria Catalysts for Electrochemical CO2 Reduction","authors":"Jianing Mao,Guanghui Feng,Bingbao Mei,Ziran Xu,Yiheng Wei,Xiaohu Liu,Jingyuan Ma,Fanfei Sun,Guihua Li,Yanfang Song,Xiao Dong,Wei Chen,Fei Song,Zheng Jiang","doi":"10.1021/acscatal.5c08410","DOIUrl":"https://doi.org/10.1021/acscatal.5c08410","url":null,"abstract":"Low-valence copper species (Cuδ+, 0 < δ < 1) on Cu-based electrocatalysts are crucial for C–C coupling to form C2+ products, yet the stability of Cuδ+ especially at industrial-scale current, remains a significant challenge. Herein, we designed a strongly correlated metal–metal oxide nanosphere catalyst (Cu@CeO2–x) that stabilizes Cuδ+ species and establishes a Cu0–Cu+ interface to better regulate hydrogen adsorption, achieving a maximum faradaic efficiency for C2+ products of 82.5% at 300 mA cm–2 and −0.62 VRHE, while maintaining stable CO2 reduction reaction performance for over 72 h. Operando X-ray absorption fine structure and in-situ Raman spectroscopy indicated that Cu@CeO2–x underwent in-situ surface reconstruction, enabling a CeO2-mediated Cuδ+ redox cycle. This dynamic charge equilibrium forms a Cu0–Cu+ interface through the self-sacrifice of Ce sites to avoid an immoderate reduction of Cu. Furthermore, density functional calculations together with in-situ attenuated total reflection–surface-enhanced infrared absorption spectroscopy indicated that Cu0–Cu+ interface enhances *CO adsorption, and facilitates C–C coupling for C2+ products formation. The findings provide a blueprint for designing Cu-based electrocatalysts to combat rapid deactivation, enhancing performance toward higher-value products.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138521","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 : 2026-02-09DOI: 10.1021/acscatal.6c00006
Qiaoyu Zhang,Xiaoyu Wang,Huining Ji,Binju Wang
Flavoenzymes play a crucial role in biotransformation processes, particularly in the metabolism of sulfur-containing compounds. Despite extensive studies, the mechanism of selective C–S bond cleavage catalyzed by flavoenzymes is not yet fully explored. Here, using extensive molecular dynamics (MD) simulations and QM/MM and QM calculations, our studies reveal that flavin-N5OOH carries out the selective C–H bond deprotonation of the substrate by releasing the strong base of hydroxyl anions (OH–), which leads to the highly electrophilic flavin-N5O intermediate for the further oxygenation of the substrate carbon anion. The synergistic base-catalysis by flavin-N5OOH and electrophilic oxidation by flavin-N5O enable the C–S bond cleavage of methanesulfonate (MS–) in MsuD and the desulfurization reaction of N-acetyl-S-alkyl-l-cysteine sulfoxide (NASAC-SO) in CmoJ. The proposed mechanism is consistent with isotope labeling experiments. We assume that such a synergistic mechanism can be applied to other types of C–S bond cleavage catalyzed by flavoenzymes, including SsuD, SfnG, and DmoA. These findings expand our understanding of oxygen activation chemistry in flavoenzymes and highlight the general catalytic mechanism across the superfamily of sulfur-metabolizing flavoenzymes.
{"title":"Double Active Species in Flavoenzymes-Catalyzed C–S Bond Cleavage: Synergistic Base-Catalysis by Flavin-N5OOH and Electrophilic Oxidation by Flavin-N5O","authors":"Qiaoyu Zhang,Xiaoyu Wang,Huining Ji,Binju Wang","doi":"10.1021/acscatal.6c00006","DOIUrl":"https://doi.org/10.1021/acscatal.6c00006","url":null,"abstract":"Flavoenzymes play a crucial role in biotransformation processes, particularly in the metabolism of sulfur-containing compounds. Despite extensive studies, the mechanism of selective C–S bond cleavage catalyzed by flavoenzymes is not yet fully explored. Here, using extensive molecular dynamics (MD) simulations and QM/MM and QM calculations, our studies reveal that flavin-N5OOH carries out the selective C–H bond deprotonation of the substrate by releasing the strong base of hydroxyl anions (OH–), which leads to the highly electrophilic flavin-N5O intermediate for the further oxygenation of the substrate carbon anion. The synergistic base-catalysis by flavin-N5OOH and electrophilic oxidation by flavin-N5O enable the C–S bond cleavage of methanesulfonate (MS–) in MsuD and the desulfurization reaction of N-acetyl-S-alkyl-l-cysteine sulfoxide (NASAC-SO) in CmoJ. The proposed mechanism is consistent with isotope labeling experiments. We assume that such a synergistic mechanism can be applied to other types of C–S bond cleavage catalyzed by flavoenzymes, including SsuD, SfnG, and DmoA. These findings expand our understanding of oxygen activation chemistry in flavoenzymes and highlight the general catalytic mechanism across the superfamily of sulfur-metabolizing flavoenzymes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138523","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}
Metal–organic frameworks (MOFs) and their derived catalysts are attractive for carbon dioxide (CO2) electroreduction to carbon monoxide (CO) but face challenges, including salt precipitation in neutral/alkaline electrolytes and poor selectivity in acidic media. Herein, we conducted in situ electrochemical pretreatment on the Ag MOF of Ag5(pyridine-3,5-dicarboxylic acid)2(OH) (AgPyDC) to form derived AgPyDC/Ag electrocatalysts with heterostructures between Ag nanoparticles (NPs) and residual MOFs, which prevent salt precipitation and enhance catalytic activity in acidic CO2 electroreduction. AgPyDC/Ag electrocatalysts exhibit a CO Faradaic efficiency (FE) of 91% and long-term stability over 50 h at pH = 3, whereas the CO FE of Ag NPs is only 38%, which indicates that such AgPyDC/Ag heterostructures can greatly enhance selectivity and stability. X-ray photoelectron spectroscopy reveals that such AgPyDC/Ag heterostructures exhibit a more electron-rich Ag state than Ag NPs. In situ Raman spectroscopy reveals that such AgPyDC/Ag heterostructures facilitate CO2 activation, while the interfacial water structure highlights a stable interfacial K+ concentration that underpins efficient CO production. This work not only provides a cost-effective pathway toward acidic CO2 electroreduction but also offers mechanistic insights into MOF-derived structures that enhance catalytic activity, guiding advanced catalyst design.
{"title":"Derived MOF/Ag Electrocatalysts for Selective and Stable CO Production during Acidic CO2 Electroreduction","authors":"Can-Jun Zou,Wei Tang,Jing-Jing Li,Cheng-Yu Zhang,Jian-Hua Jia,Ping-Ping Fang","doi":"10.1021/acscatal.5c07881","DOIUrl":"https://doi.org/10.1021/acscatal.5c07881","url":null,"abstract":"Metal–organic frameworks (MOFs) and their derived catalysts are attractive for carbon dioxide (CO2) electroreduction to carbon monoxide (CO) but face challenges, including salt precipitation in neutral/alkaline electrolytes and poor selectivity in acidic media. Herein, we conducted in situ electrochemical pretreatment on the Ag MOF of Ag5(pyridine-3,5-dicarboxylic acid)2(OH) (AgPyDC) to form derived AgPyDC/Ag electrocatalysts with heterostructures between Ag nanoparticles (NPs) and residual MOFs, which prevent salt precipitation and enhance catalytic activity in acidic CO2 electroreduction. AgPyDC/Ag electrocatalysts exhibit a CO Faradaic efficiency (FE) of 91% and long-term stability over 50 h at pH = 3, whereas the CO FE of Ag NPs is only 38%, which indicates that such AgPyDC/Ag heterostructures can greatly enhance selectivity and stability. X-ray photoelectron spectroscopy reveals that such AgPyDC/Ag heterostructures exhibit a more electron-rich Ag state than Ag NPs. In situ Raman spectroscopy reveals that such AgPyDC/Ag heterostructures facilitate CO2 activation, while the interfacial water structure highlights a stable interfacial K+ concentration that underpins efficient CO production. This work not only provides a cost-effective pathway toward acidic CO2 electroreduction but also offers mechanistic insights into MOF-derived structures that enhance catalytic activity, guiding advanced catalyst design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"45 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138520","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}
Skeletal rearrangement serves as a fundamental mechanism for generating sesterterpenoid structural diversity, yet the enzymatic control of these processes remains poorly understood. Here, by integrating AlphaFold2-predicted structural models with site-directed mutagenesis, we identify a single residue (Phe92/Ile92) on the D-helix of fungal sesterterpene synthase ZbSS that acts as a master modulator of skeletal rearrangement. The I92F mutation in ZbSS effectively reprogrammed its outcome, unlocking a rearrangement to produce the pentacyclic dia-quiannulatenes, a mechanism supported by prior DFT calculations. This represents the successful rational reprogramming of skeletal rearrangement in fungal bifunctional terpene synthases via a single residue. MD simulations further suggested that Phe92 steers the carbocation fate via stabilizing cation−π interactions. Our approach establishes a strategy for expanding terpene diversity through engineered skeletal rearrangements.
{"title":"Engineering the D-Helix in Fungal Sesterterpene Synthase ZbSS Unlocks a Skeletal Rearrangement Cyclization Route toward Sesterterpene Diversification","authors":"Weiyan Zhang,Kaitong Peng,Keying Lan,Song-Wei Li,Yanye Zhang,Wujue Xu,Yuwei Chen,Tom Hsiang,Yue-Wei Guo,Lixin Zhang,Xueting Liu","doi":"10.1021/acscatal.5c07482","DOIUrl":"https://doi.org/10.1021/acscatal.5c07482","url":null,"abstract":"Skeletal rearrangement serves as a fundamental mechanism for generating sesterterpenoid structural diversity, yet the enzymatic control of these processes remains poorly understood. Here, by integrating AlphaFold2-predicted structural models with site-directed mutagenesis, we identify a single residue (Phe92/Ile92) on the D-helix of fungal sesterterpene synthase ZbSS that acts as a master modulator of skeletal rearrangement. The I92F mutation in ZbSS effectively reprogrammed its outcome, unlocking a rearrangement to produce the pentacyclic dia-quiannulatenes, a mechanism supported by prior DFT calculations. This represents the successful rational reprogramming of skeletal rearrangement in fungal bifunctional terpene synthases via a single residue. MD simulations further suggested that Phe92 steers the carbocation fate via stabilizing cation−π interactions. Our approach establishes a strategy for expanding terpene diversity through engineered skeletal rearrangements.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"94 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138518","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 : 2026-02-09DOI: 10.1021/acscatal.5c07724
Min Yu,Dachen Ouyang,Xiaojun Zhao,Zhenxing Ren,Fei Yao,Liqiang Wang,You-Nian Liu
In the cascade hydrogenation reaction of nitroarenes to hydroxylamines, followed by the conversion of hydroxylamines to anilines, overcoming the hydroxylamine selectivity–activity trade-off imposed by the linear scaling relations remains challenging. Here, alloying Pt with an oxophilic metal (OM) (e.g., Fe, Co, and Ni) can disrupt such linear scaling relations, enabling high hydroxylamine yields without the additives typically required by conventional catalysts. Using Pt3Co/AC as a primary model, experimental and density functional theory (DFT) calculations demonstrate that the high performance in nitroarene reduction to hydroxylamine is ascribed to the asymmetric adsorption of the −NO2 group, i.e., one N–O bond binds at Pt sites and the other at Co, which spatially decouples cleavage of the initial N–O bond from subsequent desorption/hydrogenation of N–O-containing intermediates, thereby disrupting the linear scaling relation between nitrobenzene and N-phenylhydroxylamine (N-PHA). On Pt sites, cleavage of the first N–O bond in −NO2 (rate-determining step) proceeds with a reduced barrier. In contrast, hydrogenation of N-PHA on Co is kinetically less favorable than its desorption. Collectively, these effects yield high N-PHA selectivity without loss of activity. A similar trend was observed for PtFe/AC and PtNi/AC, both of which exhibit better performance than their Pt/AC counterpart.
{"title":"Breaking Scaling Relations for Selective N-Phenylhydroxylamine Synthesis on Platinum Catalysts via Oxophilic Metal Alloying-Induced Asymmetric Adsorption of −NO2","authors":"Min Yu,Dachen Ouyang,Xiaojun Zhao,Zhenxing Ren,Fei Yao,Liqiang Wang,You-Nian Liu","doi":"10.1021/acscatal.5c07724","DOIUrl":"https://doi.org/10.1021/acscatal.5c07724","url":null,"abstract":"In the cascade hydrogenation reaction of nitroarenes to hydroxylamines, followed by the conversion of hydroxylamines to anilines, overcoming the hydroxylamine selectivity–activity trade-off imposed by the linear scaling relations remains challenging. Here, alloying Pt with an oxophilic metal (OM) (e.g., Fe, Co, and Ni) can disrupt such linear scaling relations, enabling high hydroxylamine yields without the additives typically required by conventional catalysts. Using Pt3Co/AC as a primary model, experimental and density functional theory (DFT) calculations demonstrate that the high performance in nitroarene reduction to hydroxylamine is ascribed to the asymmetric adsorption of the −NO2 group, i.e., one N–O bond binds at Pt sites and the other at Co, which spatially decouples cleavage of the initial N–O bond from subsequent desorption/hydrogenation of N–O-containing intermediates, thereby disrupting the linear scaling relation between nitrobenzene and N-phenylhydroxylamine (N-PHA). On Pt sites, cleavage of the first N–O bond in −NO2 (rate-determining step) proceeds with a reduced barrier. In contrast, hydrogenation of N-PHA on Co is kinetically less favorable than its desorption. Collectively, these effects yield high N-PHA selectivity without loss of activity. A similar trend was observed for PtFe/AC and PtNi/AC, both of which exhibit better performance than their Pt/AC counterpart.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"22 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138519","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 : 2026-02-09DOI: 10.1021/acscatal.5c06198
You-yi Sun,Zhengxin Yang,You-li Sun,Rui-quan Yu,Alexey Y. Ganin
Phase-pure antiperovskite nitrides (A3XN; A = Co, Ni; X = Zn, In, Sn) synthesized via a melamine method were evaluated as cost-effective, high-performance hydrogen evolution reaction (HER) electrocatalysts. Initial tests in 1 M NaOH electrolyte revealed limited activity, significantly enhanced by reductive electrochemical cycling, attributed to the in situ formation of catalytically active zero-valent Co0 and Ni0 surface species. Comparative studies of isostructural Fe-based nitrides confirmed that these metallic A-site species constitute the active sites. Accelerated stability tests (95 °C, 10 M NaOH) identified Co3ZnN and Ni3ZnN as particularly robust, maintaining intact antiperovskite structures and high catalytic activity (>70 mA cm–2 after 210 h). Partial substitution (Zn for In) further improved stability, notably for Ni3Zn0.25In0.75N. This study highlights the crucial role of compositional tuning and surface activation in optimizing HER performance, emphasizing that systematic stability assessments under industrially relevant conditions (high temperature, concentrated electrolyte) are essential. Antiperovskite nitrides thus offer promising avenues for scalable, green hydrogen production technologies.
{"title":"Antiperovskite Nitrides as Efficient and Durable Electrocatalysts for Industrially Relevant Hydrogen Evolution","authors":"You-yi Sun,Zhengxin Yang,You-li Sun,Rui-quan Yu,Alexey Y. Ganin","doi":"10.1021/acscatal.5c06198","DOIUrl":"https://doi.org/10.1021/acscatal.5c06198","url":null,"abstract":"Phase-pure antiperovskite nitrides (A3XN; A = Co, Ni; X = Zn, In, Sn) synthesized via a melamine method were evaluated as cost-effective, high-performance hydrogen evolution reaction (HER) electrocatalysts. Initial tests in 1 M NaOH electrolyte revealed limited activity, significantly enhanced by reductive electrochemical cycling, attributed to the in situ formation of catalytically active zero-valent Co0 and Ni0 surface species. Comparative studies of isostructural Fe-based nitrides confirmed that these metallic A-site species constitute the active sites. Accelerated stability tests (95 °C, 10 M NaOH) identified Co3ZnN and Ni3ZnN as particularly robust, maintaining intact antiperovskite structures and high catalytic activity (>70 mA cm–2 after 210 h). Partial substitution (Zn for In) further improved stability, notably for Ni3Zn0.25In0.75N. This study highlights the crucial role of compositional tuning and surface activation in optimizing HER performance, emphasizing that systematic stability assessments under industrially relevant conditions (high temperature, concentrated electrolyte) are essential. Antiperovskite nitrides thus offer promising avenues for scalable, green hydrogen production technologies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"295 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138515","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 : 2026-02-09DOI: 10.1021/acscatal.5c07269
Atefeh Nadeali,Vepa Rozyyev,Jeffrey W. Elam,Saurabh N. Misal,Brian P. Chaplin
This study investigated the effect of synthesis temperature (550 to 1050 °C) on the performance of Magnéli phase titanium suboxide electrodes for electrochemical nitrate (NO3–) reduction. Different synthesis temperatures produced distinct Magnéli phases, which were characterized using X-ray diffraction and X-ray photoelectron spectroscopy. Higher temperatures increased oxygen vacancy and Ti3+ concentrations. The electrode synthesized at 850 °C consisted of a mixed Magnéli phase with predominant Ti9O17 structure and demonstrated the highest NO3– removal (∼60%) and low nitrite selectivity (∼2.8%) at −0.8 V/SHE with an 8.3 s hydraulic residence time (pH ∼8). This electrode achieved a Faradaic efficiency of 72% for ammonia production at −1.4 V/SHE with 100 mM NO3– concentration. The pseudo-first-order rate constant (172 h–1) exceeded those of other nonprecious and precious metal electrodes, attributed to the high specific surface area per volume (∼1.3 × 106 m–1) and efficient mass transfer enabled by the flow-through reactor design. Superior performance was attributed to optimized electronic properties, including band gap (1.31 eV) and flat band potential (−1.10 V/SHE), which facilitated efficient electron transfer at the electrode/electrolyte interface. These results underscore the critical role of synthesis temperature in tuning the electrochemical properties of Magnéli phase electrodes, providing insights for developing efficient, nonprecious-metal-based electrodes for nitrate remediation.
{"title":"Tailoring Magnéli Phase Titanium Suboxides for Electrochemical Nitrate Reduction to Ammonium","authors":"Atefeh Nadeali,Vepa Rozyyev,Jeffrey W. Elam,Saurabh N. Misal,Brian P. Chaplin","doi":"10.1021/acscatal.5c07269","DOIUrl":"https://doi.org/10.1021/acscatal.5c07269","url":null,"abstract":"This study investigated the effect of synthesis temperature (550 to 1050 °C) on the performance of Magnéli phase titanium suboxide electrodes for electrochemical nitrate (NO3–) reduction. Different synthesis temperatures produced distinct Magnéli phases, which were characterized using X-ray diffraction and X-ray photoelectron spectroscopy. Higher temperatures increased oxygen vacancy and Ti3+ concentrations. The electrode synthesized at 850 °C consisted of a mixed Magnéli phase with predominant Ti9O17 structure and demonstrated the highest NO3– removal (∼60%) and low nitrite selectivity (∼2.8%) at −0.8 V/SHE with an 8.3 s hydraulic residence time (pH ∼8). This electrode achieved a Faradaic efficiency of 72% for ammonia production at −1.4 V/SHE with 100 mM NO3– concentration. The pseudo-first-order rate constant (172 h–1) exceeded those of other nonprecious and precious metal electrodes, attributed to the high specific surface area per volume (∼1.3 × 106 m–1) and efficient mass transfer enabled by the flow-through reactor design. Superior performance was attributed to optimized electronic properties, including band gap (1.31 eV) and flat band potential (−1.10 V/SHE), which facilitated efficient electron transfer at the electrode/electrolyte interface. These results underscore the critical role of synthesis temperature in tuning the electrochemical properties of Magnéli phase electrodes, providing insights for developing efficient, nonprecious-metal-based electrodes for nitrate remediation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"132 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138517","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 : 2026-02-09DOI: 10.1021/acscatal.5c08638
Hong-Hao Zhang,Dan Yang,Tian-Zhen Li,Jia-Liang Yang,Fang-Xi Liu,Zi-Yun Zou,Feng Shi
Axially chiral (hetero)biaryl halides represent important structural motifs in functional molecules and synthetic chemistry. While catalytic atroposelective halogenation offers a direct route to such scaffolds, existing approaches predominantly rely on electrophilic halogenating reagents. However, the use of stable and benign nucleophilic halogen sources─particularly for chlorination─remains underdeveloped. Herein, we report a dual photoredox-nickel-catalyzed atroposelective nucleophilic chlorination of racemic heterobiaryl triflates employing chloride ions as the nucleophile. This method affords axially chiral heterobiaryl chlorides in high yields with high enantioselectivity. The choice of photocatalyst governs the reaction pathway, enabling selective product formation through either kinetic resolution (KR) or dynamic kinetic asymmetric transformation (DyKAT). Furthermore, the resulting enantioenriched heterobiaryl chlorides undergo diverse transformations via C–Cl bond cleavage, yielding a range of functionalized heterobiaryl atropisomers and underscoring the synthetic utility of this methodology. Mechanistic investigations suggest the involvement of an energy transfer process and elucidate the distinct kinetic profiles associated with the KR and DyKAT pathways. This work advances catalytic atroposelective nucleophilic chlorination, establishes a photoredox/Ni-cocatalyzed asymmetric C–Cl coupling, and offers a flexible strategy for the enantioselective synthesis of halogenated atropisomers through switchable KR or DyKAT processes.
{"title":"Catalytic Atroposelective Nucleophilic Chlorination for the Synthesis of Chlorinated Atropisomers via Dual Photoredox/Nickel Catalysis","authors":"Hong-Hao Zhang,Dan Yang,Tian-Zhen Li,Jia-Liang Yang,Fang-Xi Liu,Zi-Yun Zou,Feng Shi","doi":"10.1021/acscatal.5c08638","DOIUrl":"https://doi.org/10.1021/acscatal.5c08638","url":null,"abstract":"Axially chiral (hetero)biaryl halides represent important structural motifs in functional molecules and synthetic chemistry. While catalytic atroposelective halogenation offers a direct route to such scaffolds, existing approaches predominantly rely on electrophilic halogenating reagents. However, the use of stable and benign nucleophilic halogen sources─particularly for chlorination─remains underdeveloped. Herein, we report a dual photoredox-nickel-catalyzed atroposelective nucleophilic chlorination of racemic heterobiaryl triflates employing chloride ions as the nucleophile. This method affords axially chiral heterobiaryl chlorides in high yields with high enantioselectivity. The choice of photocatalyst governs the reaction pathway, enabling selective product formation through either kinetic resolution (KR) or dynamic kinetic asymmetric transformation (DyKAT). Furthermore, the resulting enantioenriched heterobiaryl chlorides undergo diverse transformations via C–Cl bond cleavage, yielding a range of functionalized heterobiaryl atropisomers and underscoring the synthetic utility of this methodology. Mechanistic investigations suggest the involvement of an energy transfer process and elucidate the distinct kinetic profiles associated with the KR and DyKAT pathways. This work advances catalytic atroposelective nucleophilic chlorination, establishes a photoredox/Ni-cocatalyzed asymmetric C–Cl coupling, and offers a flexible strategy for the enantioselective synthesis of halogenated atropisomers through switchable KR or DyKAT processes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"31 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138522","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 : 2026-02-08DOI: 10.1021/acscatal.5c09228
Lorenzo Agosta,Giuseppe Zollo,Annabella Selloni
Brookite TiO2, a rare natural polymorph of TiO2, has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (ObrH) and terminal hydroxyls (Ti–OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti3+) sites, while Ti–OH groups prefer to form at the 4-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.
{"title":"Insights into the Reactivity of Brookite TiO2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations","authors":"Lorenzo Agosta,Giuseppe Zollo,Annabella Selloni","doi":"10.1021/acscatal.5c09228","DOIUrl":"https://doi.org/10.1021/acscatal.5c09228","url":null,"abstract":"Brookite TiO2, a rare natural polymorph of TiO2, has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (ObrH) and terminal hydroxyls (Ti–OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti3+) sites, while Ti–OH groups prefer to form at the 4-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138524","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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