ACS Catalysis 最新文献

{"title":"On-Demand Metal-to-Metal Electron Donation during Zr–Ru Heterodinuclear-Catalyzed Amine–Borane Dehydrogenation","authors":"Jugal Kumawat, Daniel H. Ess","doi":"10.1021/acscatal.4c03724","DOIUrl":"https://doi.org/10.1021/acscatal.4c03724","url":null,"abstract":"Dinuclear metal–metal cooperative effects are important in catalysis involving the activation of small molecules with strong bonds. Here, we report density functional theory calculations used to determine the catalytic mechanism and metal–metal cooperative effects during amine–borane dehydrogenation catalyzed by a Zr–Ru heterodinuclear complex. These calculations revealed that, during catalysis bond activation, steps occur mainly at the Zr center and the Ru metal plays a role as a ligand-like on-demand electron donation partner. We also used calculations to determine the mechanistic and reactivity differences between the dinuclear Zr–Ru complex and mononuclear Zr and Ru complexes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562169","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}

{"title":"Bifunctional Metal–Organic Layer for Selective Photocatalytic Carbon Dioxide Reduction to Carbon Monoxide","authors":"Yingling Liao, Zitong Wang, Jinhong Li, Yingjie Fan, David Wang, Li Shi, Wenbin Lin","doi":"10.1021/acscatal.4c04772","DOIUrl":"https://doi.org/10.1021/acscatal.4c04772","url":null,"abstract":"We report a bifunctional metal–organic layer (MOL) as a photocatalyst for CO₂ reduction to CO under visible light irradiation with a turnover number of 6990 in 24 h and a CO selectivity of 99%. The fully accessible and modifiable Hf₁₂ secondary building units and the coordinating porphyrin linkers of the MOL allow for the integration of both Ru photosensitizers and catalytic Fe-porphyrin sites into one single platform. The close distance (∼11 Å) between the Ru photosensitizer and the catalytic center leads to enhanced electron transfer and promotes photocatalytic CO₂ reduction. This strategy leads to an increase of the CO₂-to-CO turnover number for the bifunctional MOL catalyst over a combination of a homogeneous Ru photosensitizer and an Fe-porphyrin complex. The mechanism of MOL-catalyzed CO₂ photoreduction was also studied by photophysical and electrochemical experiments.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563219","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}

{"title":"Selective and Efficient Light-Driven CO2 Reduction to CO with a Heptacoordinated Polypyridine Iron(II) Catalyst","authors":"Federico Droghetti, Florian Lemken, Lubomír Rulíšek, Albert Ruggi, Mirco Natali","doi":"10.1021/acscatal.4c04290","DOIUrl":"https://doi.org/10.1021/acscatal.4c04290","url":null,"abstract":"The selective generation of carbon-based products in the presence of proton donors currently represents one of the major goals in the catalysis of the CO₂ reduction reaction (CO₂RR). Within this framework, the iron complex of the 1-([2,2′-bipyridin]-6-yl)-<i>N</i>-([2,2′-bipyridin]-6-ylmethyl)-<i>N</i>-(pyridin-2-ylmethyl) methanamine ligand (DBPy-PyA) turns out to be a selective and efficient catalyst to promote the conversion of CO₂ into CO. In the present work, we report a detailed experimental and computational investigation of the CO₂RR by this metal complex. Efficient formation of CO (selectivity &gt;90%) was attained under electrochemical conditions (applied potential of −2.0 V vs Fc⁺/Fc) using trifluoroethanol as the proton donor, which provides the best balance, among those tested, in terms of Lewis and Brønsted acidity. This is indeed instrumental in accelerating CO₂ activation while minimizing the parallel generation of hydrogen byproduct. The high activity and selectivity toward CO formation were shown to arise from (i) the ability of the ligand to assist via intramolecular routes the formation of the metallacarboxylic acid catalytic intermediate, (ii) the favorable and almost barrierless detachment of the CO product from the putative iron(II) carbonyl intermediate, and (iii) the weak tendency of the two-electron-reduced complex to form the metal-hydride species. The CO₂RR by the titled complex was further investigated under light-driven catalytic conditions with [Ru(bpy)₃]²⁺ (bpy = 2,2′-bipyridine) as the sensitizer and <i>N</i>,<i>N</i>-diisopropylethylamine (DIPEA) as the electron donor, leading to unprecedented performances under 1 sun irradiation (0.85 mL CO per mL of solution, quantum yield of 9.4%, selectivity &gt;97%, solely limited by degradation of the sensitizer). Transient absorption spectroscopy suggested that, for the three-component photochemical system examined, catalyst activation by the photogenerated reductant represents the rate-determining step of the photosynthetic process. With this information in hand, by carefully modulating the photon flux, we succeeded in achieving a more than 3-fold enhancement in the quantum yield of CO formation (up to 28%). All in all, our study showcases the great, but often underestimated, potential of molecular catalysis to target efficient and selective transformations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561988","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}

{"title":"Unveiling the Pivotal Role of Ce Coordination Structures and Their Surface Arrangements in Governing 2-Cyanopyridine Hydrolysis for Direct Dimethyl Carbonate Synthesis from CO2 and Methanol","authors":"Linyuan Tian, Yin-Song Liao, Zhanping Xiao, Guohan Sun, Jyh-Pin Chou, Chun-Yuen Wong, Johnny C. Ho, Yufei Zhao, Pi-Tai Chou, Yung-Kang Peng","doi":"10.1021/acscatal.4c04639","DOIUrl":"https://doi.org/10.1021/acscatal.4c04639","url":null,"abstract":"The direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol presents a promising alternative to conventional methods that use toxic chemicals, but its yield is limited by equilibrium. Coupling this reaction with 2-cyanopyridine (2-Cp) hydrolysis over CeO₂-based catalysts was found to significantly boost the DMC yield by removing water. Our recent study has revealed that methanol is the key species being activated by surface Ce sites to produce DMC. The reactivity of surface methoxy species toward CO₂ varies greatly with their configuration, which is determined by the Ce coordination structures. A similar challenge remains in understanding the CeO₂ surface feature governing the hydrolysis of 2-Cp to 2-picolinamide (2-PA). Herein, CeO₂ nanocrystallites with well-defined (111), (110), and (100) surfaces were used to study the effects of Ce coordination structures and their arrangements in this reaction and coupled DMC synthesis. We found that the synergistic adsorption of 2-Cp via cyano-N and pyridine-N on (111) and (110) surfaces enables nucleophilic addition of lattice oxygen, producing imino-like N with stronger Lewis basicity, which in turn facilitates hydrolysis. The (111) surface outperforms the (110) surface due to its unique Ce coordination structure and arrangement, which allows more 2-Cp activation and easier 2-PA desorption. Notably, the (111)-enclosed octahedral CeO₂ used herein outperforms the reported pristine CeO₂ catalysts in this coupled reaction. In contrast, this synergistic adsorption/activation does not occur on the (100) surface, leading to low activity. These findings provide insights for designing CeO₂-based catalysts for CO₂ conversion with alcohols and amines using 2-Cp as a dehydrant.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561746","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}

{"title":"Oxidative Catalytic Fractionation of Lignocellulose Enhanced by Copper–Manganese-Doped CeO2","authors":"Yuting Zhu, Ning Li, Huifang Liu, Cheng Cai, Yehong Wang, Junju Mu, Feng Wang","doi":"10.1021/acscatal.4c04159","DOIUrl":"https://doi.org/10.1021/acscatal.4c04159","url":null,"abstract":"Oxidative catalytic fractionation (OCF) represents an efficient approach to valorize lignocellulose for coproduction of monophenols and cellulose. To achieve an adequate monophenol yield, lignin oxidation, typically, requires high O₂ pressure and an excess of Cu catalysts (the Cu dosage is approximately 3–5 mol equiv relative to the aromatic units in lignin). However, these conditions are relatively harsh for cellulose, resulting in severe decomposition to aliphatic acids. To address the trade-off between the monophenol yield and cellulose production, we develop an enhanced OCF using a CuMnCeO₂ solid solution as the catalyst. Under relatively mild conditions (specifically, 0.1 MPa O₂), 28.7 wt % monophenols were released from birch, using catalytic amounts of Cu (the Cu dosage was about 0.03 mol equiv relative to the aromatic units in lignin). Meanwhile, up to 83.9% of cellulose was collected as a solid pulp. The synergistic effect between doped metals (Cu and Mn) and oxygen vacancies was found to be crucial for enhanced lignin oxidation under mild conditions with minimized cellulose loss. The abundant surface oxygen vacancies facilitated oxygen activation by well-dispersed Cu and Mn species, while the strong interaction between these metals enhanced the catalyst’s reducibility. Key intermediates such as β-vinyl aryl ethers and byproduct glycolic acid were identified by model experiments, confirming that lignin oxidation primarily followed a 1,2-dioxetane homolysis mechanism. Overall, this enhanced OCF demonstrates the potential viability of lignin oxidation in practical biorefinery applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561987","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}

{"title":"pH-Mediated Solution-Phase Proton Transfer Drives Enhanced Electrochemical Hydrogenation of Phenol in Alkaline Electrolyte","authors":"Brianna Markunas, Taber Yim, Joshua Snyder","doi":"10.1021/acscatal.4c04874","DOIUrl":"https://doi.org/10.1021/acscatal.4c04874","url":null,"abstract":"The faradaic efficiency (FE) of the electrochemical hydrogenation (ECH) of phenol and other biomass-derived model compounds could potentially be improved by operating in alkaline electrolytes, where the parasitic hydrogen evolution reaction rate is significantly slower due to a higher Volmer step barrier. However, this approach is potentially limited by the impact of the higher barrier for adsorbed hydrogen (H_ad) formation, as hydrocarbon ECH is expected to be limited by a hydrogen atom transfer, progressing through a Langmuir–Hinshelwood-type (LH) mechanism. In this work, we show that there are contrasting pH trends for phenol ECH between Pt and Rh, two common catalysts for ECH reactions. Phenol ECH FE and rate on Pt is highest in acidic electrolytes of pH ≤ 5, while activity on Rh is highest near pH 9–10. While our kinetic analysis supports a LH mechanism for Pt at all pH, phenol ECH on Rh shifts from a LH mechanism at low pH to being limited by a direct proton-coupled electron transfer (Eley–Rideal-type mechanism) in which surface adsorbed phenol is hydrogenated by solution-phase H-transfer. We show that the peak activity on Rh at pH 9–10 is due to the proximity of the pH to the p<i>K</i>_a of phenol (p<i>K</i>_a = 10.0). The reversibility of protonation/deprotonation of phenol when electrolyte pH matches its p<i>K</i>_a helps to mediate H-transfer from solution to adsorbed phenol. We also discuss the role of buffer species in mitigating the local pH change and as a H-donor in phenol ECH on Rh at alkaline pH.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562170","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}

{"title":"An Unusual His/Asp Dyad Operates Catalysis in Agar-Degrading Glycosidases","authors":"Mert Sagiroglugil, Alba Nin-Hill, Elizabeth Ficko-Blean, Carme Rovira","doi":"10.1021/acscatal.4c04139","DOIUrl":"https://doi.org/10.1021/acscatal.4c04139","url":null,"abstract":"Agarose motifs, found in agars present in the cell walls of red algae, consist of alternating units of <span>d</span>-galactose (G) and α-3,6-anhydro-<span>l</span>-galactose (LA). Glycoside hydrolases from family 117 (GH117) cleave the terminal α-1,3-glycosidic bonds, releasing LA units. Structural studies have suggested that these enzymes use unconventional catalytic machinery, involving a histidine (His302) as a general acid rather than a carboxylic residue as in most glycosidases. By means of quantum mechanics/molecular mechanics metadynamics, we investigated the reaction mechanism of <i>Phocaeicola plebeius</i> GH117, confirming the catalytic role of His302. This residue shares a proton with a neighbor aspartate residue (Asp320), forming a His/Asp dyad. Our study also reveals that, even though the sugar unit at the <i>–1</i> subsite (LA) can adopt two conformations, ⁴<i>C</i>₁ and ^1,4<i>B</i>, only the latter is catalytically competent, defining a ^1,4<i>B</i> → [⁴<i>E</i>]^‡ → ^1,4<i>B</i> (→ ⁴<i>C</i>₁) conformational itinerary. This mechanism may be applicable to similar enzymes with a His/Asp dyad in their active sites, such as GH3 β-<i>N</i>-acetylglucosaminidase and GH156 sialidase. These insights enhance our understanding of glycosidase catalytic strategies and could inform the engineering of enzymes for the more efficient processing of seaweed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562172","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}

{"title":"Heterogeneous Catalytic Transformation of Biomass-Derived Furans to Selectively Produce C4 Chemicals with the Simulated Sunlight","authors":"Xiaoqian Gao, Hang Tang, Xinli Tong, Jiaxin Zheng","doi":"10.1021/acscatal.4c04204","DOIUrl":"https://doi.org/10.1021/acscatal.4c04204","url":null,"abstract":"Catalytic transformation of biomass resources to synthesize the value-added C₄ chemicals has attracted wide attention in the catalysis field. In this work, with the metal organic frameworks (MOFs) as the heterogeneous catalyst, the biobased furans including furoic acid (FAC) and furfuryl alcohol (FAL) were selectively transformed to 5-hydroxy-2(5<i>H</i>)-furanone (HFO) and succinic anhydride (SAN) in the presence of molecular oxygen. For instance, a 99.0% conversion with 95.6% selectivity of SAN was obtained by using Hf-TCPP as a photocatalyst under the optimal conditions. The EPR detection showed that generation of singlet oxygen plays a crucial role in the conversion of furanic derivatives. Moreover, the recycling experiments verified that these catalysts can remain stable and are reusable in the photocatalytic reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556387","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}

{"title":"Relative Generality and Risk: Quantitative Measures for Broad Catalyst Success","authors":"Michal Sanocki, Hayley C. Russell, Jasemine Handjaya, Jolene P. Reid","doi":"10.1021/acscatal.4c04395","DOIUrl":"https://doi.org/10.1021/acscatal.4c04395","url":null,"abstract":"The performance of chiral catalysts is typically evaluated against empirical reaction outputs like yield and selectivity with traditional analyses limited to a single model system. Expansion of the reaction space permits catalysts to be assessed for generality, and this provides another useful metric for measuring the effectiveness of a catalyst. The catalyst generality algorithm will assign quantitative generality values to catalyst structures, but such broad assessments are applied with the assumption that the reactions under evaluation are more or less the same by disregarding any inherent challenges associated with a particular reaction class. To address this limitation, we introduce two metrics: relative generality and risk. These are designed to correct for variations in reaction difficulty and enable a more nuanced evaluation of the catalyst performance relative to the specific demands of each reaction. We show in a number of challenging examples that these metrics allow researchers to distinguish between catalysts genuinely exhibiting superior performance and those appearing favorable due to application toward less demanding reactions. This represents a significant advancement in quantifying catalyst success with demonstrated applications in retrospective analyses and early insights into emerging catalyst classes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556056","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}

{"title":"Repurposing a Fully Reducing Polyketide Synthase toward 2-Methyl Guerbet-like Lipids","authors":"Michael A. Herrera, Stephen McColm, Louise-Marie Craigie, Joanna Simpson, Fraser Brown, David J. Clarke, Reuben Carr, Dominic J. Campopiano","doi":"10.1021/acscatal.4c04714","DOIUrl":"https://doi.org/10.1021/acscatal.4c04714","url":null,"abstract":"In nature, thousands of diverse and bioactive polyketides are assembled by a family of multifunctional, “assembly line” enzyme complexes called polyketide synthases (PKS). Since the late 20th century, there have been several attempts to decode, rearrange, and “reprogram” the PKS assembly line to generate valuable materials such as biofuels and platform chemicals. Here, the first module from <i>Mycobacterium tuberculosis</i> (<i>Mt</i>) PKS12, an unorthodox, “modularly iterative” PKS, was modified and repurposed toward the formation of 2-methyl Guerbet lipids, which have wide applications in industry. We established a robust method for the recombinant expression and purification of this modified module (named [M₁*]), and we demonstrated its ability to catalyze the formation of several 2-methyl Guerbet-like lipids (C₁₃–C₂₁). Furthermore, we studied and applied the promiscuous thioesterase activity of a neighboring β-ketoacyl synthase (KS) to release [M₁*]-bound condensation products in a one-pot biosynthetic cascade. Finally, starting from lauric acid, we could generate our primary target compound (2-methyltetradecanoic acid) by coupling the <i>Escherichia coli</i> fatty acyl-CoA synthetase FadD to [M₁*]. This work supports the biosynthetic utility of engineered PKS modules such as [M₁*] and their ability to derive valuable Guerbet-like lipids from inexpensive fatty acids.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556233","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}