Review
Chemistry, Multidisciplinary
Chenxi Wen, Ting Li, Zheng Huang, Qi-Kai Kang
Summary: Preparing valuable olefins from cheap and abundant alkane resources has long been a challenging task in organic synthesis. Homogeneous transition metals catalyzed dehydrogenation of alkanes has attracted much attention for its excellent catalytic activities. In this review, we discuss recent development of base metal catalyzed alkane dehydrogenation under oxidative conditions and their application in constructing complex molecules.
Article
Chemistry, Physical
Zhe Li, Tobias K. Misicko, Fan Yang, Xiaopeng Liu, Zhenwei Wu, Xiaoyang Gao, Tao Ma, Jeffrey T. Miller, Daniela S. Mainardi, Collin D. Wick, Zhenhua Zeng, Yang Xiao, Yue Wu
Summary: Atomically thin Pt nanolayers were synthesized and used as catalysts for the dehydrogenation of ethane and propane. The Pt nanolayer catalyst showed superior coke-resistance, high activity and selectivity compared to Pt nanoparticles. The electronic effect was found to play a critical role in product selectivity and catalyst stability, while geometric effect was negligible.
Article
Chemistry, Physical
Liang Qi, Yanfei Zhang, Melike Babucci, Cailing Chen, Peng Lu, Jingwei Li, Chaochao Dun, Adam S. Hoffman, Jeffrey J. Urban, Michael Tsapatsis, Simon R. Bare, Yu Han, Bruce C. Gates, Alexis T. Bell
Summary: The use of self-pillared pentasil zeolite nanosheets as supports for Pt catalysts enables highly active, selective, and stable catalysis in the dehydrogenation of propane and butane. The catalysts show excellent performance, with no deactivation observed after 12 days of reaction, and high selectivity for the desired products.
Article
Chemistry, Multidisciplinary
Mungo Frost, Emma E. McBride, Dean Smith, Jesse S. Smith, Siegfried H. Glenzer
Summary: Dehydrogenation of alkanes plays an increasingly important role in meeting global demand for olefins and providing a potential source of carbon-neutral hydrogen. However, current commercial processes are energy intensive and suffer from side reactions and rapid catalyst coking. This study utilizes pressure as a parameter to achieve ambient-temperature dehydrogenation of alkanes by palladium, leading to the recovery of hydrogen gas and olefins. The reaction follows a fundamentally different path from high-temperature low-pressure dehydrogenation processes, with the formation of a reversible hydride intermediate by the palladium catalyst.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Chemistry, Physical
Michaela Koenig, Michael Traxler, Maik Alexander Rudolph, Johannes Schmidt, Huseyin Kucukkececi, Reinhard Schomaecker, Arne Thomas
Summary: In this study, an iridium pincer complex was immobilized in a propyl bromide-functionalized microporous polymer network using surface organometallic chemistry. The catalyst showed high activity and stability in the continuous-flow dehydrogenation of cyclohexane at elevated temperatures.
Article
Chemistry, Physical
Lixia Wang, Bo Peng, Aiguo Zheng, Ye Song, Qiuqiao Jiang, Peng Wang, Haitao Song, Wei Lin, Mingyuan He
Summary: In this study, n-octane was used to represent the alkane content in catalytic cracking. Various techniques were used to quantify active sites, and the contribution of newly generated local acid sites to the kinetic behavior was investigated.
JOURNAL OF CATALYSIS
(2022)
Review
Chemistry, Physical
Xiaowen Chen, Mi Peng, Dequan Xiao, Hongyang Liu, Ding Ma
Summary: This article discusses the unique catalytic performance of FECCs in alkane dehydrogenation, including structure design and synthetic methods. Recent understanding of FECCs and their importance in alkane dehydrogenation is summarized, providing useful guidance for catalyst design.
Article
Energy & Fuels
Ajuan Zhou, Jiaxing Zhang, Hong Yang, Shujie Shang, Anfeng Zhang, Chunshan Song, Xinwen Guo
Summary: This study explores the rational design of Pt/ZSM-5 bifunctional catalysts for alkylating benzene with ethane. It reveals that the Si/Al ratio of ZSM-5 regulates the dispersion and particle size of Pt, and the interaction between H+ of ZSM-5 and Pt plays a crucial role in controlling the product distribution in the reaction.
Article
Chemistry, Physical
Son Dong, Natalie R. Altvater, Lesli O. Mark, Ive Hermans
Summary: Propylene, an important chemical feedstock, is traditionally produced by cracking oil-derived naphtha, but direct conversion of propane into propylene presents an attractive alternative. Propane dehydrogenation (DH) and oxidative dehydrogenation (ODH) are promising methods for this transformation, with challenges such as catalyst deactivation and lack of mechanistic understanding. Recent advancements in preparing well-defined active sites on ordered supports have led to improved catalysts and better understanding of the working mechanism.
APPLIED CATALYSIS A-GENERAL
(2021)
Review
Chemistry, Inorganic & Nuclear
Ziqiang Qu, Qiming Sun
Summary: This review summarizes the latest research progress in zeolite-supported metal catalysts for propane dehydrogenation (PDH) reactions, including synthesis methods, catalytic mechanisms, and structure-function relationships. It provides references and insights for the future design of highly efficient zeolite-supported metal catalysts for PDH applications.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Qifeng Lei, Chang Wang, Weili Dai, Guangjun Wu, Naijia Guan, Michael Hunger, Landong Li
Summary: The study prepared bifunctional TiSn-Beta zeolite as an efficient heterogeneous catalyst for converting alkenes to 1,2-diols in a single step with high selectivity. The isolated Ti and Sn Lewis acid sites within the zeolite enabled efficient integration of alkene epoxidation and epoxide hydration in tandem reactions, showing high selectivity towards the desired product. This novel method can be applied to other tandem catalytic reactions for sustainable chemical production.
CHINESE JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Carrie A. Farberow, Evan C. Wegener, Anurag Kumar, Jacob H. Miller, Daniel P. Dupuis, Seonah Kim, Daniel A. Ruddy
Summary: Ni-modified beta zeolite catalysts can activate carbon-hydrogen bonds in light alkanes and increase hydrogen production. Increasing the Ni loading enhances both alkane activation activity and the formation of hydrogen-deficient aromatic products retained within the catalyst pores. In situ diffuse-reflectance UV-visible-NIR absorbance and X-ray absorption spectroscopies reveal the presence of two distinct Ni(2+) sites with different stabilities and activities.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Santanu Malakar, Benjamin M. Gordon, Souvik Mandal, Thomas J. Emge, Alan S. Goldman
Summary: The reaction between [(p-cymene)RuCl2]2 and the triphosphine ligand bis(2-di-tert-butylphosphinophenyl)phosphine (tBuPHPP) leads to an exchange reaction where a chloride ligand and a phosphorus-bound H atom are exchanged to form the (chlorophosphine)ruthenium hydride complex (tBuPClPP)RuHCl. The thermodynamics of Cl-P/Ru-H exchange depends on the nature of the ancillary ligand. This study has implications for five-coordinate d6 complexes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Xuefei Zhang, Xueya Dai, Kuang-Hsu Wu, Bingjian Su, Jinming Chen, Wei Qi, Zailai Xie
Summary: This study presents a generalized strategy to enhance the catalytic activity of BCN by encapsulating transition-metal nanoparticles within BCN nanotubes. The metal particles act as electron modulators to tune the electron density of active sites on BCNNTs, promoting ODH reactions. Fe@BCNNTs catalyst shows significant activity enhancement in EB ODH reactions.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Jin-Soo Kim, Iljun Chung, Jungmok Oh, Jisu Park, Yongju Yun, Jungho Shin, Hyun Woo Kim, Hyunju Chang
Summary: In this study, the catalyst composition for oxidative propane dehydrogenation with CO2 (ODPC) was optimized using a machine learning model and a metaheuristic algorithm. The proposed catalysts, with enhanced performance compared to the initial database, were prepared and evaluated. The study provides a framework to optimize the chemical composition of multi-component catalysts for improved propylene yield and CO2 activity in the ODPC reaction.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Chemistry, Physical
Philip M. Kester, Enrique Iglesia, Rajamani Gounder
JOURNAL OF PHYSICAL CHEMISTRY C
(2020)
Article
Chemistry, Physical
Iker Agirrezabal-Telleria, Enrique Iglesia
JOURNAL OF CATALYSIS
(2020)
Article
Chemistry, Physical
Stephanie Kwon, Ting Chun Lin, Enrique Iglesia
JOURNAL OF PHYSICAL CHEMISTRY C
(2020)
Article
Chemistry, Physical
Edwin Yik, David Hibbitts, Huamin Wang, Enrique Iglesia
Summary: Thiophene-H2 reactions proceed on dispersed metal nanoparticles via sulfur removal and hydrogenation routes, with reaction steps influenced by H2S/H2 ratios. Strong repulsion among S adatoms leads to partial surface coverage, creating interstitial spaces for catalytic turnovers.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Physical
Ting Chun Lin, Unai De La Torre, Ava Hejazi, Stephanie Kwon, Enrique Iglesia
Summary: The study reveals a bimolecular reaction mechanism in formic acid dehydrogenation on copper surfaces. The co-existence of formate adlayers and *HCOO* moieties on the catalyst surface leads to the formation of H-bonded bimolecular HCOOH square-*HCOO* adducts, reducing the activation barriers for dehydrogenation.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Haefa Mansour, Enrique Iglesia
Summary: This study investigates the catalytic routes for upgrading CO2 to CO and hydrocarbons on dispersed Ru nanoparticles, revealing the elementary steps involved in these reactions and shedding light on the mechanism of CO2 activation. The kinetic hurdles in forming CH4 from CO2 are shown to stem not from the inertness of CO2 itself, but from the intermediate formation of CO molecules and the rate inhibition caused by chemisorbed CO. The findings are based on a combination of spectroscopic, isotopic, and kinetic measurements, highlighting the importance of considering the effects of nanoparticle structure and composition on reactivity and selectivity in CO2-H2 reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Enrique Iglesia, David Hibbitts
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Samuel L. Leung, David Hibbitts, Monica Garcia-Dieguez, Enrique Iglesia
Summary: Experimental and theoretical evidence suggests that H-2-D-2 isotopic equilibration occurs through non-competitive adsorption mechanisms at catalytic temperatures, without requiring recombinative desorption steps.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Shashikant A. Kadam, Andrew Hwang, Enrique Iglesia
Summary: This study investigates the effects of non-polar liquids on acetone aldol condensation reactions on TiO2 surfaces. The results show that non-polar liquids enhance reaction rates and selectivity by stabilizing transition states for adsorption and desorption. Additionally, solvation by non-polar liquids prevents the formation of larger oligomers, leading to slower deactivation of the catalyst.
Article
Chemistry, Physical
Trenton Otto, Xiaoyu Zhou, Stacey I. Zones, Enrique Iglesia
Summary: A synthetic procedure was developed for encapsulating Au nanoparticles within titanium silicalite-1 (TS-1), allowing for the assembly of TS-1 frameworks around Au coordination complexes. Changes to established crystallization procedures for TS-1 led to successful encapsulation of small Au nanoparticles, which showed catalytic activity for propene epoxidation.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Ari F. Fischer, Enrique Iglesia
Summary: Support effects in alkene and arene hydrogenations on metal catalysts attributed to hydrogen spillover are caused by the desorption and hydrogenation of Pt-bound intermediates at acid-base pairs on certain oxides. Toluene-H2 reactions on Pt nanoparticles dispersed on SiO2 occur on surfaces with diverse coverages and reactivity, leading to preferential occupation by less reactive isomers. These less reactive species can desorb as methylcyclohexadiene molecules, which diffuse to nearby oxide surfaces and react, increasing the abundance of more reactive intermediates at Pt surfaces.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Andrew Hwang, Jason Wu, Andrew Bean Getsoian, Enrique Iglesia
Summary: Reduction-oxidation cycles in oxides are widely used in various applications and require coupling reactions at the surfaces of oxide crystals. CeO2-ZrO2 solid solutions (CZO) were used to study the kinetic relevance of surface reactions and diffusion in O-atom addition and removal. The experiments showed that O-removal rates depend on reductant pressures, while O-addition rates are similar for different reactants and can be affected by the presence of Pt nanoparticles.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Enrique Iglesia, Haefa Mansour
Summary: Kinetic and isotopic measurements, along with theoretical assessments, were used to determine the identity and relevance of elementary steps and bound species in H-2-O-2 reactions on Pt surfaces. The reactions involve two kinetically-relevant O2 dissociation routes, one forming two bound O atoms on Pt atom ensembles within H* adlayers, and the other involving reactions with a H*-H* pair to form weakly bound hydrogen peroxide (*HOOH*). The results provide insights into the reaction mechanisms and can help improve catalytic processes.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Nicholas R. Jaegers, Enrique Iglesia
Summary: Ni-based solids are effective catalysts for alkene dimerization, and the nature of their active centers and the identity and relevance of bound species and elementary reactions have been explored. A study shows that Ni centers grafted onto ordered MCM-41 mesopores lead to stable monomers that act as Lewis acid-base pairs and stabilize C-C coupling transition states. Density functional theory (DFT) treatments confirm the involvement of these active centers and pathways, which were not previously considered. The DFT-derived activation barriers for ethene dimerization are consistent with experimental measurements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Prashant Deshlahra, Enrique Iglesia
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Physical
Yifan Sun, Ye Lv, Wei Li, Jinli Zhang, Yan Fu
Summary: In this study, PtRu electrocatalysts were fabricated on carbon paper via cyclic electrodeposition for the electrocatalytic hydrogenation (ECH) of phenol. The Pt3Ru3 catalyst exhibited excellent activity and stability for the conversion of phenol to cyclohexanol at ambient temperature and various current densities. The in situ Raman spectroscopy and kinetic study revealed the hydrogenation mechanism of phenol over Pt3Ru3 in acidic electrolyte, providing an effective electrochemical strategy for the facile construction of durable electrode materials and efficient phenol hydrogenation.
JOURNAL OF CATALYSIS
(2024)
Article
Chemistry, Physical
Amir Shahzad, Khezina Rafiq, Muhammad Zeeshan Abid, Naseem Ahmad Khan, Syed Shoaib Ahmad Shah, Raed H. Althomali, Abdul Rauf, Ejaz Hussain
Summary: Photocatalytic hydrogen production through water splitting is an effective method for meeting future energy demands. In this study, researchers synthesized a 1 % Ag2S/Cu2S co-doped CdZnS catalyst and found that it can produce hydrogen at a higher rate. The co-doping of Ag2S and Cu2S in the CdZnS catalyst showed a synergistic effect, with Ag2S promoting oxidation reactions and Cu2S promoting reduction reactions.
JOURNAL OF CATALYSIS
(2024)