Pub Date : 2026-03-20DOI: 10.1021/acscatal.6c00401
Christian Sant Gjermestad, Rin Seki, Shuhei Kusumoto, Giovanni Occhipinti, Erwan Le Roux, Kyoko Nozaki, Vidar R. Jensen
Arene-selective hydrodeoxygenation (HDO) of phenols enables the renewable production of aromatics. We examined the origin of the unusually high selectivity of the Ir(4PhCpOH)H2PPh3 precursor (Ir1, where 4PhCpOH = 1-hydroxy-tetraphenyl-cyclopentadienyl). Neither intact Ir1, its ligand-stripped molecular derivatives, nor bare iridium nanoparticles (NP) matched its performance, prompting exploration of catalyst cocktails. A readily prepared 3:1 NP-to-IrH(COD)(PPh3)2 (Ir2, where COD = 1,5-cyclooctadiene) mixture, synthetically far simpler than Ir1, delivers Ir1-like yields and selectivities for phenylphenols and can be tuned to broaden the substrate scope. Mechanistic studies show arene formation occurs directly or via partial ring hydrogenation. Ir2–NP synergy offers a route to arene-selective HDO.
{"title":"Stirred, Not Shaken: Pre-Made Catalyst Cocktail Enables Arene-Selective Hydrodeoxygenation of Phenols","authors":"Christian Sant Gjermestad, Rin Seki, Shuhei Kusumoto, Giovanni Occhipinti, Erwan Le Roux, Kyoko Nozaki, Vidar R. Jensen","doi":"10.1021/acscatal.6c00401","DOIUrl":"https://doi.org/10.1021/acscatal.6c00401","url":null,"abstract":"Arene-selective hydrodeoxygenation (HDO) of phenols enables the renewable production of aromatics. We examined the origin of the unusually high selectivity of the Ir(<sup>4Ph</sup>CpOH)H<sub>2</sub>PPh<sub>3</sub> precursor (<b>Ir1</b>, where <sup>4Ph</sup>CpOH = 1-hydroxy-tetraphenyl-cyclopentadienyl). Neither intact <b>Ir1</b>, its ligand-stripped molecular derivatives, nor bare iridium nanoparticles (<b>NP</b>) matched its performance, prompting exploration of catalyst cocktails. A readily prepared 3:1 <b>NP</b>-to-IrH(COD)(PPh<sub>3</sub>)<sub>2</sub> (<b>Ir2</b>, where COD = 1,5-cyclooctadiene) mixture, synthetically far simpler than <b>Ir1</b>, delivers <b>Ir1</b>-like yields and selectivities for phenylphenols and can be tuned to broaden the substrate scope. Mechanistic studies show arene formation occurs directly or via partial ring hydrogenation. <b>Ir2</b>–<b>NP</b> synergy offers a route to arene-selective HDO.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"85 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490019","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}
Solar-driven photoelectrochemical hydrogen production is a promising way to achieve carbon neutrality, but severe charge recombination in photoanodes limits the conversion efficiency. Herein, the conjugated polycarbazole framework (CPF-TCB) as the hole transport layer and NiFeOOH as the oxygen evolution cocatalyst are combined to simultaneously enhance the efficiency of charge separation and surface catalytic kinetics in BiVO4 photoanodes. CPF-TCB provides an appropriate energy level for rapid hole extraction while suppressing recombination, whereas NiFeOOH markedly increases the density of intermediate surface states (i-SS) to accelerate the oxygen evolution reaction. Consequently, the constructed BiVO4/CPF-TCB/NiFeOOH photoanode achieves a photocurrent density of 4.25 mA cm–2 at 1.23 VRHE and exhibits photostability for 20 h. This work provides a paradigm for exploiting the synergistic effects of organic hole transport layers and oxygen evolution cocatalysts toward efficient and durable solar-driven hydrogen production.
太阳能驱动的光电化学制氢是一种很有前途的实现碳中和的方法，但光电阳极中严重的电荷重组限制了转换效率。本文通过结合共轭聚咔唑框架（CPF-TCB）作为空穴传输层和NiFeOOH作为析氧助催化剂，同时提高了BiVO4光阳极的电荷分离效率和表面催化动力学。CPF-TCB在抑制复合的同时为快速的空穴提取提供了合适的能级，而NiFeOOH则显著增加了中间表面态（i-SS）的密度，加速了析氧反应。因此，构建的BiVO4/CPF-TCB/NiFeOOH光阳极在1.23 VRHE下实现了4.25 mA cm-2的光电流密度，并表现出20小时的光稳定性。这项工作为利用有机空穴传输层和析氧共催化剂的协同效应实现高效耐用的太阳能驱动制氢提供了一个典范。
{"title":"Enhanced Photoelectrochemical Water Splitting of BiVO4 Photoanode via Synergistic Effects of Polycarbazole Hole Transport Layer and NiFeOOH Cocatalyst","authors":"Pengfei Lv, Zhiru Xie, Guangping Yi, Yiping Zhao, Mengfan Shang, Xiaofan Yang, Sijie Wen, Zhao Jing, Qiang Wang, DongSheng Song, Pengyi Tang","doi":"10.1021/acscatal.5c09061","DOIUrl":"https://doi.org/10.1021/acscatal.5c09061","url":null,"abstract":"Solar-driven photoelectrochemical hydrogen production is a promising way to achieve carbon neutrality, but severe charge recombination in photoanodes limits the conversion efficiency. Herein, the conjugated polycarbazole framework (CPF-TCB) as the hole transport layer and NiFeOOH as the oxygen evolution cocatalyst are combined to simultaneously enhance the efficiency of charge separation and surface catalytic kinetics in BiVO<sub>4</sub> photoanodes. CPF-TCB provides an appropriate energy level for rapid hole extraction while suppressing recombination, whereas NiFeOOH markedly increases the density of intermediate surface states (i-SS) to accelerate the oxygen evolution reaction. Consequently, the constructed BiVO<sub>4</sub>/CPF-TCB/NiFeOOH photoanode achieves a photocurrent density of 4.25 mA cm<sup>–2</sup> at 1.23 V<sub>RHE</sub> and exhibits photostability for 20 h. This work provides a paradigm for exploiting the synergistic effects of organic hole transport layers and oxygen evolution cocatalysts toward efficient and durable solar-driven hydrogen production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490018","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 : 2026-03-20DOI: 10.1021/acscatal.6c00291
Kelin Li, Juan Lopez, Zion Kang, Ziwei Wang, Sha Hu, Tao Zhang, Xufeng Fang, Blair Szymczyna, Mark W. Grinstaff, Pinghua Liu
6-Thioguanosine 5′-monophosphate (6-TGMP) is the biologically active nucleotide form of the antimetabolite 6-thioguanine produced by Erwinia amylovorans. The YcfA-YcfC enzymatic pair catalyzes the incorporation of the thioamide functional group in GMP via an oxygen-to-sulfur replacement process. YcfA is a member of the adenine nucleotide alpha hydrolase-like (AANH-like) superfamily, and YcfC is a pyridoxal 5′-phosphate (PLP)-dependent enzyme. Two mechanistic models exist, depending on whether YcfC is a C–S lyase or a cysteine desulfurase, to explain the trans-sulfuration reaction. Herein, we investigate the YcfA-YcfC trans-sulfuration reaction using anaerobically purified YcfA and YcfC enzymes in the absence of reductants. Steady state and presteady state kinetic studies suggest the mechanism involves two distinct intermediates and differs from the common trans-sulfuration pathway used in, for example, tRNA thionucleotide biosynthesis.
{"title":"Biosynthesis of 6-Thioguanine: Characterizing Two Intermediates Involved in Its Thioamide Formation Reaction","authors":"Kelin Li, Juan Lopez, Zion Kang, Ziwei Wang, Sha Hu, Tao Zhang, Xufeng Fang, Blair Szymczyna, Mark W. Grinstaff, Pinghua Liu","doi":"10.1021/acscatal.6c00291","DOIUrl":"https://doi.org/10.1021/acscatal.6c00291","url":null,"abstract":"6-Thioguanosine 5′-monophosphate (6-TGMP) is the biologically active nucleotide form of the antimetabolite 6-thioguanine produced by <i>Erwinia amylovorans</i>. The YcfA-YcfC enzymatic pair catalyzes the incorporation of the thioamide functional group in GMP via an oxygen-to-sulfur replacement process. YcfA is a member of the adenine nucleotide alpha hydrolase-like (AANH-like) superfamily, and YcfC is a pyridoxal 5′-phosphate (PLP)-dependent enzyme. Two mechanistic models exist, depending on whether YcfC is a C–S lyase or a cysteine desulfurase, to explain the trans-sulfuration reaction. Herein, we investigate the YcfA-YcfC trans-sulfuration reaction using anaerobically purified YcfA and YcfC enzymes in the absence of reductants. Steady state and presteady state kinetic studies suggest the mechanism involves two distinct intermediates and differs from the common trans-sulfuration pathway used in, for example, tRNA thionucleotide biosynthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492514","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 : 2026-03-19DOI: 10.1021/acscatal.5c09187
Alfred Vargas, Gaurav A. Kamat, Judith Zander, Ashton M. Aleman, Johanna Schröder, Ryan T. Hannagan, Aniket S. Mule, Milenia Rojas Mendoza, Colin F. Crago, Daniela H. Marin, Peter Benedek, Joseph T. Perryman, Lingze Wei, Charline Rémy, Yamilet Margarita Rivera Cintrón, Vivek Thampy, Thomas F. Jaramillo
The electrode–electrolyte interface plays a large role in steering electrocatalytic activity, selectivity, and stability. However, there is limited understanding of the general structure and dynamics of the reactive microenvironment and its effects on electrocatalyst performance. Herein, this study probes the effects of acid anion identity (pH 1, HClO4, HNO3, H2SO4, HCl, HBr) on Pd electrocatalyst stability, surface morphology, and crystal structure during the oxygen reduction reaction (ORR), using a multimodal in situ approach. The overall trend in Pd stability follows: HClO4 > HNO3 ∼H2SO4 > HCl ≫ HBr, paralleling observed ORR activity, highlighting the correlation between stability and electrocatalytic performance. To correlate the stability trends with ORR activity, dissolution rates were quantified using on-line inductively coupled plasma mass spectrometry (ICP-MS) under ORR-relevant conditions. Complementary in situ X-ray reflectivity (XRR) closely agrees with trends observed from on-line ICP-MS, while atomic force microscopy (AFM) revealed corresponding surface roughening behavior. In situ grazing incidence X-ray diffraction (GIXRD) further revealed facet-specific peak broadening for the (200), indicating early signs of anisotropic amorphization and potentially a route toward dissolution. Altogether, this work establishes a multimodal in situ framework for understanding anion-dependent dissolution and surface reconstruction of electrocatalysts under ORR operating conditions. These insights enable rational electrolyte design for enhanced stability in acidic media, bridging interfacial science with strategies to promote electrocatalyst durability and activity in concert.
{"title":"Multimodal In Situ Investigation of Anion-Dependent Surface Dynamics of Pd Electrocatalysts during the Oxygen Reduction Reaction in Acidic Media","authors":"Alfred Vargas, Gaurav A. Kamat, Judith Zander, Ashton M. Aleman, Johanna Schröder, Ryan T. Hannagan, Aniket S. Mule, Milenia Rojas Mendoza, Colin F. Crago, Daniela H. Marin, Peter Benedek, Joseph T. Perryman, Lingze Wei, Charline Rémy, Yamilet Margarita Rivera Cintrón, Vivek Thampy, Thomas F. Jaramillo","doi":"10.1021/acscatal.5c09187","DOIUrl":"https://doi.org/10.1021/acscatal.5c09187","url":null,"abstract":"The electrode–electrolyte interface plays a large role in steering electrocatalytic activity, selectivity, and stability. However, there is limited understanding of the general structure and dynamics of the reactive microenvironment and its effects on electrocatalyst performance. Herein, this study probes the effects of acid anion identity (pH 1, HClO<sub>4</sub>, HNO<sub>3</sub>, H<sub>2</sub>SO<sub>4</sub>, HCl, HBr) on Pd electrocatalyst stability, surface morphology, and crystal structure during the oxygen reduction reaction (ORR), using a multimodal <i>in situ</i> approach. The overall trend in Pd stability follows: HClO<sub>4</sub> > HNO<sub>3</sub> ∼H<sub>2</sub>SO<sub>4</sub> > HCl ≫ HBr, paralleling observed ORR activity, highlighting the correlation between stability and electrocatalytic performance. To correlate the stability trends with ORR activity, dissolution rates were quantified using on-line inductively coupled plasma mass spectrometry (ICP-MS) under ORR-relevant conditions. Complementary <i>in situ</i> X-ray reflectivity (XRR) closely agrees with trends observed from on-line ICP-MS, while atomic force microscopy (AFM) revealed corresponding surface roughening behavior. <i>In situ</i> grazing incidence X-ray diffraction (GIXRD) further revealed facet-specific peak broadening for the (200), indicating early signs of anisotropic amorphization and potentially a route toward dissolution. Altogether, this work establishes a multimodal <i>in situ</i> framework for understanding anion-dependent dissolution and surface reconstruction of electrocatalysts under ORR operating conditions. These insights enable rational electrolyte design for enhanced stability in acidic media, bridging interfacial science with strategies to promote electrocatalyst durability and activity in concert.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"115 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490021","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 : 2026-03-19DOI: 10.1021/acscatal.5c07786
Jim Mensah, Deshetti Jampaiah, Ravindra Kokate, Priyank Kumar, Inna Karatchevtseva, Yingjie Zhang, Michael Moir, Tamim Darwish
Metal-catalyzed hydrothermal deuteration is a versatile approach for hydrogen–deuterium exchange (HDE) reactions, offering precise isotopic labeling of organic molecules. Here, we report the development of a scalable flow deuteration method that permits the tunable isotopic selectivity of saturated short-chain fatty acids over platinum group metal (PGM) catalysts. Benchmarking against conventional batch hydrothermal deuteration in pressurized vessels demonstrated that flow deuteration sustains high steady-state activity, improves single-pass yields, and provides mechanistic insights into isotopologue formation. Under optimized conditions, 10 wt % Pt/C achieved 93% D (deuterium incorporation) and 98% isolated yield of sodium butyrate-d7 in 90 min time-on-stream (TOS) under H2-free conditions (20 bar D2O, 220 °C) in a single pass. Notably, flow deuteration afforded high selectivity to -d7 (60%) and -d6 (32%) isotopologues and favored the formation of thermodynamically stable isotopologues at elevated temperatures, as confirmed by isotopologue analysis (MS) and isotopomer distribution (NMR). The intrinsic activity of Pt (TOF = 6 h–1) exceeds that of Pd metal (with similar loading) by an order of magnitude, determined at iso-conversion (<20% conversion under differential reactor conditions). In situ catalyst activation allowed for four consecutive reaction cycles without loss of activity, with the catalyst maintaining stability over 540 min of time-on-stream. Density functional theory calculations revealed a facile and preferential α–C–H activation of butyric acid via cooperative C- and O-metal interactions on Pt, effectively lowering activation barriers at other C-sites and thereby promoting perdeuteration compared to Pd. Process intensification under flow conditions resulted in a 4-fold increase in the production rate, underscoring the potential of this approach for the scalable, selective, and operationally efficient synthesis of deuterated short-chain fatty acids. This work presents a viable blueprint for platform-specific isotopic labeling using flow chemistry.
{"title":"Flow-Enabled Deuteration of Saturated Fatty Acids over Platinum Group Metals: Mechanistic and Process Insights","authors":"Jim Mensah, Deshetti Jampaiah, Ravindra Kokate, Priyank Kumar, Inna Karatchevtseva, Yingjie Zhang, Michael Moir, Tamim Darwish","doi":"10.1021/acscatal.5c07786","DOIUrl":"https://doi.org/10.1021/acscatal.5c07786","url":null,"abstract":"Metal-catalyzed hydrothermal deuteration is a versatile approach for hydrogen–deuterium exchange (HDE) reactions, offering precise isotopic labeling of organic molecules. Here, we report the development of a scalable flow deuteration method that permits the tunable isotopic selectivity of saturated short-chain fatty acids over platinum group metal (PGM) catalysts. Benchmarking against conventional batch hydrothermal deuteration in pressurized vessels demonstrated that flow deuteration sustains high steady-state activity, improves single-pass yields, and provides mechanistic insights into isotopologue formation. Under optimized conditions, 10 wt % Pt/C achieved 93% D (deuterium incorporation) and 98% isolated yield of sodium butyrate-<i>d</i><sub>7</sub> in 90 min time-on-stream (TOS) under H<sub>2</sub>-free conditions (20 bar D<sub>2</sub>O, 220 °C) in a single pass. Notably, flow deuteration afforded high selectivity to -<i>d</i><sub>7</sub> (60%) and -<i>d</i><sub>6</sub> (32%) isotopologues and favored the formation of thermodynamically stable isotopologues at elevated temperatures, as confirmed by isotopologue analysis (MS) and isotopomer distribution (NMR). The intrinsic activity of Pt (TOF = 6 h<sup>–1</sup>) exceeds that of Pd metal (with similar loading) by an order of magnitude, determined at iso-conversion (<20% conversion under differential reactor conditions). In situ catalyst activation allowed for four consecutive reaction cycles without loss of activity, with the catalyst maintaining stability over 540 min of time-on-stream. Density functional theory calculations revealed a facile and preferential α–C–H activation of butyric acid via cooperative C- and O-metal interactions on Pt, effectively lowering activation barriers at other C-sites and thereby promoting perdeuteration compared to Pd. Process intensification under flow conditions resulted in a 4-fold increase in the production rate, underscoring the potential of this approach for the scalable, selective, and operationally efficient synthesis of deuterated short-chain fatty acids. This work presents a viable blueprint for platform-specific isotopic labeling using flow chemistry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"401 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492515","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 : 2026-03-19DOI: 10.1021/acscatal.5c09080
Yifeng Wang, Liam P. Twight, Nicole A. Sagui, Minkyoung Kwak, Shannon W. Boettcher, Benjamin S. Moss, Ifan E. L. Stephens, James R. Durrant, Reshma R. Rao
NixFe1–xOyHz is the state-of-the-art catalyst for the oxygen evolution reaction (OER) in alkaline water electrolyzers; however, understanding the impact of Fe on the active sites, reaction mechanism, and consequently intrinsic activity has been under intense debate. In this work, operando UV–vis spectroscopy was used to investigate Fe-free NiOxHy and NiOxHy with Fe selectively incorporated onto the surface. At oxygen-evolution potentials, similar oxidized nickel states were present before and after the Fe incorporation, with negligible changes in their redox potentials. However, the discharge kinetics of the Ni states show a substantial acceleration after the introduction of Fe, consistent with an increase in OER kinetics upon Fe incorporation and formation of active Ni–Fe species. Using optical spectroscopy, we determined the intrinsic reaction time constant per surface Fe site is <0.1 s, which is 2 orders of magnitude faster than Ni sites not in proximity to surface Fe sites (∼10 s), and also an order of magnitude faster than Ni sites in pure NiOxHy (∼1 s). Consequently, we propose that the OER occurs via charge accumulation primarily on Ni centers in these catalysts, followed by hole transport to the surface Fe species where oxygen evolution occurs.
{"title":"Spectroelectrochemical Studies of Oxygen Evolution Reaction Kinetics for Surface-Incorporated Iron in Nickel Oxyhydroxide Electrocatalysts","authors":"Yifeng Wang, Liam P. Twight, Nicole A. Sagui, Minkyoung Kwak, Shannon W. Boettcher, Benjamin S. Moss, Ifan E. L. Stephens, James R. Durrant, Reshma R. Rao","doi":"10.1021/acscatal.5c09080","DOIUrl":"https://doi.org/10.1021/acscatal.5c09080","url":null,"abstract":"Ni<sub><i>x</i></sub>Fe<sub>1–<i>x</i></sub>O<sub><i>y</i></sub>H<sub><i>z</i></sub> is the state-of-the-art catalyst for the oxygen evolution reaction (OER) in alkaline water electrolyzers; however, understanding the impact of Fe on the active sites, reaction mechanism, and consequently intrinsic activity has been under intense debate. In this work, <i>operando</i> UV–vis spectroscopy was used to investigate Fe-free NiO<sub><i>x</i></sub>H<sub><i>y</i></sub> and NiO<sub><i>x</i></sub>H<sub><i>y</i></sub> with Fe selectively incorporated onto the surface. At oxygen-evolution potentials, similar oxidized nickel states were present before and after the Fe incorporation, with negligible changes in their redox potentials. However, the discharge kinetics of the Ni states show a substantial acceleration after the introduction of Fe, consistent with an increase in OER kinetics upon Fe incorporation and formation of active Ni–Fe species. Using optical spectroscopy, we determined the intrinsic reaction time constant per surface Fe site is <0.1 s, which is 2 orders of magnitude faster than Ni sites not in proximity to surface Fe sites (∼10 s), and also an order of magnitude faster than Ni sites in pure NiO<sub><i>x</i></sub>H<sub><i>y</i></sub> (∼1 s). Consequently, we propose that the OER occurs via charge accumulation primarily on Ni centers in these catalysts, followed by hole transport to the surface Fe species where oxygen evolution occurs.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"240 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492516","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 : 2026-03-19DOI: 10.1021/acscatal.6c00643
Zhishan Li, Dong Tian, Xingyun Li, Zeshan Wang, Zhiqiang Li, Lei Jiang, Danyang Li, Hua Wang, Kongzhai Li
Perovskite oxides have been recognized as attractive oxygen carriers in chemical looping technologies due to their good oxygen storage capacity and redox stability, but they usually show poor activity at relatively low temperatures (≤800 °C). Herein, we modify LaFeO3 via Ni doping to facilitate chemical looping partial oxidation of methane into syngas at moderate temperatures (600–700 °C). The optimized LaFe0.93Ni0.07O3 oxygen carrier shows a methane conversion of 49.9% at 600 °C, a stark contrast to the LaFeO3 under the same condition. At 700 °C, the methane conversion increases to 88.2%, with the syngas selectivity at 84.8%. The migration of Ni from the perovskite bulk to the surface in the early state of the reaction creates active sites for methane activation. Density functional theory calculations reveal that the enhanced catalytic performance can be attributed to the incorporation of Ni into the LaFeO3 lattice, which weakens the Fe–O bond and promotes the formation of oxygen vacancies, thereby increasing lattice oxygen mobility. We also found that the methane oxidation follows a carbon intermediate pathway, where methane decomposes to the carbon intermediate and then reacts with the lattice oxygen of the oxygen carrier to form CO. The presence of Ni species can regulate the reaction pathway via promoting the formation of the carbon intermediate and lattice oxygen mobility, therefore enhancing the activity for partial oxidation of methane to syngas. Our work develops an efficient Ni-containing oxygen carrier for chemical looping partial oxidation of methane at moderate temperatures. It also provides in-depth mechanistic insight into methane oxidation by lattice oxygen, especially the role of the carbon intermediate.
{"title":"Deciphering the Dual Roles of Nickel in Perovskite Oxygen Carriers for Partial Oxidation of Methane at Moderate Temperature","authors":"Zhishan Li, Dong Tian, Xingyun Li, Zeshan Wang, Zhiqiang Li, Lei Jiang, Danyang Li, Hua Wang, Kongzhai Li","doi":"10.1021/acscatal.6c00643","DOIUrl":"https://doi.org/10.1021/acscatal.6c00643","url":null,"abstract":"Perovskite oxides have been recognized as attractive oxygen carriers in chemical looping technologies due to their good oxygen storage capacity and redox stability, but they usually show poor activity at relatively low temperatures (≤800 °C). Herein, we modify LaFeO<sub>3</sub> via Ni doping to facilitate chemical looping partial oxidation of methane into syngas at moderate temperatures (600–700 °C). The optimized LaFe<sub>0.93</sub>Ni<sub>0.07</sub>O<sub>3</sub> oxygen carrier shows a methane conversion of 49.9% at 600 °C, a stark contrast to the LaFeO<sub>3</sub> under the same condition. At 700 °C, the methane conversion increases to 88.2%, with the syngas selectivity at 84.8%. The migration of Ni from the perovskite bulk to the surface in the early state of the reaction creates active sites for methane activation. Density functional theory calculations reveal that the enhanced catalytic performance can be attributed to the incorporation of Ni into the LaFeO<sub>3</sub> lattice, which weakens the Fe–O bond and promotes the formation of oxygen vacancies, thereby increasing lattice oxygen mobility. We also found that the methane oxidation follows a carbon intermediate pathway, where methane decomposes to the carbon intermediate and then reacts with the lattice oxygen of the oxygen carrier to form CO. The presence of Ni species can regulate the reaction pathway via promoting the formation of the carbon intermediate and lattice oxygen mobility, therefore enhancing the activity for partial oxidation of methane to syngas. Our work develops an efficient Ni-containing oxygen carrier for chemical looping partial oxidation of methane at moderate temperatures. It also provides in-depth mechanistic insight into methane oxidation by lattice oxygen, especially the role of the carbon intermediate.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"113 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492517","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 : 2026-03-19DOI: 10.1021/acscatal.6c00286
Charles W. P. Pare, Aybike Terzi, Christian Kunkel, Michael Geske, Raoul Naumann d’Alnoncourt, Christoph Scheurer, Frank Rosowski, Karsten Reuter
Extending throughput capabilities and advanced sampling approaches are strongly accelerating catalyst discovery, increasingly performed within automated self-driving laboratories. The larger the tractable design spaces become though, the more questionable is the lasting value of individual optimal catalysts that are identified in black-box searches. Here, we demonstrate a sparse sampling approach that combines search efficiency with chemically interpretable insight into the topology of the design space. Applied to the nonoxidative propane dehydrogenation reaction, it readily finds pareto-optimal multipromoter formulations that exceed the present industry reference in both yield toward the desired commodity product propylene and catalyst longevity. At the same time, it explains this improved performance in terms of individual promoter effects and synergistic promoter interactions. The latter interactions are missed in prevalent empirical single-promoter studies and are shown here as a key element toward further performance gains expected upon insight-motivated future modifications of the design space.
{"title":"Adaptive Experiment Planning for Inverse Design and Understanding: Synergistic Interactions as Key to Optimized Multi-Promoter Formulations","authors":"Charles W. P. Pare, Aybike Terzi, Christian Kunkel, Michael Geske, Raoul Naumann d’Alnoncourt, Christoph Scheurer, Frank Rosowski, Karsten Reuter","doi":"10.1021/acscatal.6c00286","DOIUrl":"https://doi.org/10.1021/acscatal.6c00286","url":null,"abstract":"Extending throughput capabilities and advanced sampling approaches are strongly accelerating catalyst discovery, increasingly performed within automated self-driving laboratories. The larger the tractable design spaces become though, the more questionable is the lasting value of individual optimal catalysts that are identified in black-box searches. Here, we demonstrate a sparse sampling approach that combines search efficiency with chemically interpretable insight into the topology of the design space. Applied to the nonoxidative propane dehydrogenation reaction, it readily finds pareto-optimal multipromoter formulations that exceed the present industry reference in both yield toward the desired commodity product propylene and catalyst longevity. At the same time, it explains this improved performance in terms of individual promoter effects and synergistic promoter interactions. The latter interactions are missed in prevalent empirical single-promoter studies and are shown here as a key element toward further performance gains expected upon insight-motivated future modifications of the design space.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"52 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147477997","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 : 2026-03-19DOI: 10.1021/acscatal.5c08100
Elinor Morris, Boris Lozhkin, Jan Uhrhan, Indrek Kalvet, Sophie Basler, Roman P. Jakob, David Baker, Thomas R. Ward
Artificial metalloenzymes (ArMs) offer a versatile and evolvable platform to extend the biocatalytic repertoire. Here we report the assembly of an ArM resulting from supramolecular anchoring an N-heterocyclic carbene Au(I) complex into a de novo designed tandem repeat protein (TRP). We identified a variant that, compared to the free cofactor, led to a higher catalytic activity for the Au-catalyzed hydroamination of 2-ethynylaniline. Structure-guided mutagenesis of this variant improved the activity, resulting in a double mutant displaying up to 4-fold higher catalytic rates than the original TRP. Biophysical and crystallographic analysis revealed distinct cofactor binding poses, with single mutations reshaping the active site and correlating with improved catalytic performance. Importantly, the TRP scaffold imparted robustness, preserving catalytic activity under acidic conditions, in the presence of organic cosolvent, and at elevated temperatures, where the free cofactor was deactivated. This work highlights the potential of de novo designed proteins to harbor non-natural metal cofactors and points to design principles for stabilizing sensitive catalysts under chaotropic conditions.
{"title":"Design, Optimization and Characterization of a de novo Gold Hydroaminase","authors":"Elinor Morris, Boris Lozhkin, Jan Uhrhan, Indrek Kalvet, Sophie Basler, Roman P. Jakob, David Baker, Thomas R. Ward","doi":"10.1021/acscatal.5c08100","DOIUrl":"https://doi.org/10.1021/acscatal.5c08100","url":null,"abstract":"Artificial metalloenzymes (ArMs) offer a versatile and evolvable platform to extend the biocatalytic repertoire. Here we report the assembly of an ArM resulting from supramolecular anchoring an <i>N</i>-heterocyclic carbene Au(I) complex into a <i>de novo</i> designed tandem repeat protein (TRP). We identified a variant that, compared to the free cofactor, led to a higher catalytic activity for the Au-catalyzed hydroamination of 2-ethynylaniline. Structure-guided mutagenesis of this variant improved the activity, resulting in a double mutant displaying up to 4-fold higher catalytic rates than the original TRP. Biophysical and crystallographic analysis revealed distinct cofactor binding poses, with single mutations reshaping the active site and correlating with improved catalytic performance. Importantly, the TRP scaffold imparted robustness, preserving catalytic activity under acidic conditions, in the presence of organic cosolvent, and at elevated temperatures, where the free cofactor was deactivated. This work highlights the potential of <i>de novo</i> designed proteins to harbor non-natural metal cofactors and points to design principles for stabilizing sensitive catalysts under chaotropic conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147477999","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 : 2026-03-19DOI: 10.1021/acscatal.6c01007
Tianyao He, Yuzhen Zhang, Gan Li, Xiang Tu, Fengqing Zhuo, Jian Ji, Fengbo Yu, Guobo Li, Wenming Liu, Lu Wei, Jiguang Deng, Weili Dai, Honggen Peng
We report the rational design and precise construction of Y zeolite-encapsulated Pd catalysts featuring coexisting single atoms and clusters (Pd1+n@Y) that enable the efficient and low-temperature total oxidation of propane. Fine tuning of Pd loading and synthesis conditions in a PVP-assisted one-pot hydrothermal approach affords controllable confinement of dual active sites (isolated Pd single atoms and clusters). Catalytic evaluations reveal that Pd1+n@Y exhibits a T90 of only 265 °C, significantly outperforming the single-site counterparts (Pd1@Y and Pdn@Y). Combining density functional theory (DFT) calculations with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies elucidates a stepwise synergistic mechanism wherein Pd single atoms preferentially activate the C–H bond in propane to form alkyl intermediates, while Pd clusters facilitate O2 activation and C–C bond cleavage to complete oxidation. This work establishes a robust “single atom–cluster” synergistic paradigm for designing advanced catalysts for the abatement of light alkanes.
{"title":"Zeolite Y-Encapsulated Pd Single Atoms and Clusters: Unlocking Stepwise Synergy for Low-Temperature Propane Oxidation","authors":"Tianyao He, Yuzhen Zhang, Gan Li, Xiang Tu, Fengqing Zhuo, Jian Ji, Fengbo Yu, Guobo Li, Wenming Liu, Lu Wei, Jiguang Deng, Weili Dai, Honggen Peng","doi":"10.1021/acscatal.6c01007","DOIUrl":"https://doi.org/10.1021/acscatal.6c01007","url":null,"abstract":"We report the rational design and precise construction of Y zeolite-encapsulated Pd catalysts featuring coexisting single atoms and clusters (Pd<sub>1+<i>n</i></sub>@Y) that enable the efficient and low-temperature total oxidation of propane. Fine tuning of Pd loading and synthesis conditions in a PVP-assisted one-pot hydrothermal approach affords controllable confinement of dual active sites (isolated Pd single atoms and clusters). Catalytic evaluations reveal that Pd<sub>1+<i>n</i></sub>@Y exhibits a T<sub>90</sub> of only 265 °C, significantly outperforming the single-site counterparts (Pd<sub>1</sub>@Y and Pd<sub><i>n</i></sub>@Y). Combining density functional theory (DFT) calculations with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies elucidates a stepwise synergistic mechanism wherein Pd single atoms preferentially activate the C–H bond in propane to form alkyl intermediates, while Pd clusters facilitate O<sub>2</sub> activation and C–C bond cleavage to complete oxidation. This work establishes a robust “single atom–cluster” synergistic paradigm for designing advanced catalysts for the abatement of light alkanes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"20 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478059","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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