Browse Articles

  • Article |

    Single-atom catalysts hold great promise for process optimization by reducing metal utilization. However, their structure–activity properties remain elusive. Here, a combination of operando techniques and density functional theory analysis is used to capture the evolution of single platinum atoms on CeO2 during CO, C3H6 and CH4 oxidation.

    • Florian Maurer
    • , Jelena Jelic
    • , Junjun Wang
    • , Andreas Gänzler
    • , Paolo Dolcet
    • , Christof Wöll
    • , Yuemin Wang
    • , Felix Studt
    • , Maria Casapu
    •  & Jan-Dierk Grunwaldt
  • Article |

    Carbonyl–olefin metathesis reactions are a valuable tool in synthetic chemistry, but there are still some limitations in scope. Now, a catalyst system allows the activation of previously unreactive substrates for such a reaction by aluminium(iii)–ion pairs acting as Lewis acidic superelectrophiles.

    • Ashlee J. Davis
    • , Rebecca B. Watson
    • , Daniel J. Nasrallah
    • , Jessica L. Gomez-Lopez
    •  & Corinna S. Schindler
  • Article |

    Visualizing catalytic processes at the nanoscale is crucial to establish structure–activity relations, but remains very challenging. Here, hydrogen spillover is revealed with a 10 nm spatial resolution during hydrogenation of chloronitrobenzenethiol on a bimetallic Pd/Au catalyst by means of tip-enhanced Raman spectroscopy.

    • Hao Yin
    • , Li-Qing Zheng
    • , Wei Fang
    • , Yin-Hung Lai
    • , Nikolaus Porenta
    • , Guillaume Goubert
    • , Hua Zhang
    • , Hai-Sheng Su
    • , Bin Ren
    • , Jeremy O. Richardson
    • , Jian-Feng Li
    •  & Renato Zenobi
  • News & Views |

    The activity and the stability of an electrocatalyst are equally important, but the reasons behind deactivation processes still remain unresolved. Achieving a deeper understanding of the process will help to inhibit deactivation and improve revivification protocols.

    • Alessandro Minguzzi
  • Review Article |

    Peroxygenases are promising enzymes to contribute to more environmentally friendly and sustainable oxidation reactions in industry. This Review Article gives a comprehensive overview about enzymes with peroxygenase activity and strategies to engineer them for desired reactions and enhanced performances.

    • Marie-Cathérine Sigmund
    •  & Gerrit J. Poelarends
  • Article |

    Hydroformylation of alkenes is widely used in industry to synthesize aldehydes, but is less prominent in small laboratories due to safety and equipment issues associated with the CO/H2 mixture. This is now addressed by generating stoichiometric syngas from two main element compounds, with water as the activator.

    • Samuel K. Pedersen
    • , Haraldur G. Gudmundsson
    • , Dennis U. Nielsen
    • , Bjarke S. Donslund
    • , Hans Christian D. Hammershøj
    • , Kim Daasbjerg
    •  & Troels Skrydstrup
  • Article |

    CO is a key intermediate in the electro-oxidation of energy carrying fuels which typically acts as a poison. Here, the authors demonstrate that Cu is an efficient CO electro-oxidation catalyst in alkaline electrolyte due to the continuous formation of undercoordinated active Cu adatom sites in the presence of CO and OH.

    • Andrea Auer
    • , Mie Andersen
    • , Eva-Maria Wernig
    • , Nicolas G. Hörmann
    • , Nico Buller
    • , Karsten Reuter
    •  & Julia Kunze-Liebhäuser
  • Article |

    CRISPR–Cas9 systems have revolutionized the field of genome editing. This work reports rare structures of a Cas9 enzyme (St1Cas9) in its HNH catalytic state, providing mechanistic insights related to DNA recognition and cleavage, and structure-guided engineering is used for expansion of the PAM recognition.

    • Yifei Zhang
    • , Hongyuan Zhang
    • , Xuexia Xu
    • , Yujue Wang
    • , Weizhong Chen
    • , Yannan Wang
    • , Zhaowei Wu
    • , Na Tang
    • , Yu Wang
    • , Suwen Zhao
    • , Jianhua Gan
    •  & Quanjiang Ji
  • Article |

    The electrochemical reduction of CO2 to value-added fuels and feedstocks has recently received a great deal of attention. Here, Cu nanowires that display rich surface steps are reported to sustain C2H4 production from CO2 with a remarkably high Faradaic efficiency for 200 hours.

    • Chungseok Choi
    • , Soonho Kwon
    • , Tao Cheng
    • , Mingjie Xu
    • , Peter Tieu
    • , Changsoo Lee
    • , Jin Cai
    • , Hyuck Mo Lee
    • , Xiaoqing Pan
    • , Xiangfeng Duan
    • , William A. Goddard III
    •  & Yu Huang
  • Article |

    The fundamental kinetics of the electrocatalytic sulfur reduction reaction, a complex 16-electron conversion process in lithium–sulfur batteries, is a topic that remains largely unexplored. Here, by directly profiling the activation energies in the multi-step reaction, the authors establish how the conversion kinetics differ for each step.

    • Lele Peng
    • , Ziyang Wei
    • , Chengzhang Wan
    • , Jing Li
    • , Zhuo Chen
    • , Dan Zhu
    • , Daniel Baumann
    • , Haotian Liu
    • , Christopher S. Allen
    • , Xiang Xu
    • , Angus I. Kirkland
    • , Imran Shakir
    • , Zeyad Almutairi
    • , Sarah Tolbert
    • , Bruce Dunn
    • , Yu Huang
    • , Philippe Sautet
    •  & Xiangfeng Duan
  • Article |

    Achieving long-term stability of water oxidation electrocatalysts remains a formidable challenge. Now, an in situ electrochemical reduction strategy to revivify mixed Ni–Fe hydroxide catalysts by reversible phase segregation is presented.

    • Chunguang Kuai
    • , Zhengrui Xu
    • , Cong Xi
    • , Anyang Hu
    • , Zhijie Yang
    • , Yan Zhang
    • , Cheng-Jun Sun
    • , Luxi Li
    • , Dimosthenis Sokaras
    • , Cunku Dong
    • , Shi-Zhang Qiao
    • , Xi-Wen Du
    •  & Feng Lin
  • Article |

    Platinum dissolution and restructuring due to surface oxidation are primary degradation mechanisms of platinum-based electrocatalysts. Now, stark differences are reported in the mechanism for the oxidative extraction of platinum atoms on (111) and (100) single crystals, providing a detailed explanation for the enhanced dissolution on the latter surface.

    • Timo Fuchs
    • , Jakub Drnec
    • , Federico Calle-Vallejo
    • , Natalie Stubb
    • , Daniel J. S. Sandbeck
    • , Martin Ruge
    • , Serhiy Cherevko
    • , David A. Harrington
    •  & Olaf M. Magnussen
  • Article |

    Site-selective installation of fluorine (19F) and its radioisotope (18F) in aromatic molecules can lead to high-value products, but methods for this purpose are not without limitations. Now, using photochemistry, a 19F- and 18F- labelling strategy is reported that complements traditional approaches.

    • Nicholas E. S. Tay
    • , Wei Chen
    • , Alison Levens
    • , Vincent A. Pistritto
    • , Zeng Huang
    • , Zhanhong Wu
    • , Zibo Li
    •  & David A. Nicewicz
  • News & Views |

    Suppressing the degradation of polymer electrolyte membrane fuel cells due to anode side-reactions during repetitive cell start-up/shut-down remains a formidable challenge. Now, a phase transition material of WO3 has been explored as a smart catalytic switch to enable highly selective electrocatalysis and improve fuel cell longevity.

    • Yifei Sun
    •  & Shriram Ramanathan
  • Comment |

    Two different types of H2O2 selectivity are reported for the electrochemical synthesis of H2O2: molar fraction selectivity and Faradaic selectivity. Here we revisit their definitions and discuss the best way to report H2O2 selectivity, which can help to avoid misunderstandings or unfair performance comparisons in this growing field.

    • Chuan Xia
    • , Jung Yoon (Timothy) Kim
    •  & Haotian Wang
  • Article |

    Axial chirality is found in many important compounds, such as bioactive molecules and catalytic components. Now palladium and chiral norbornene cooperative catalysis is reported for the construction of atropisomeric biaryls and chiral fluorenols.

    • Ze-Shui Liu
    • , Yu Hua
    • , Qianwen Gao
    • , Yuanyuan Ma
    • , Hua Tang
    • , Yong Shang
    • , Hong-Gang Cheng
    •  & Qianghui Zhou
  • Article |

    The reductive deuteration of unsaturated hydrocarbons is a promising deuterium-labelling strategy, although it requires expensive gaseous D2 or other stoichiometric reagents. Here, an electrocatalytic palladium membrane reactor is employed to selectively generate C(sp3)–D bonds via reduction of unsaturated compounds using D2O.

    • Aiko Kurimoto
    • , Rebecca S. Sherbo
    • , Yang Cao
    • , Nicholas W. X. Loo
    •  & Curtis P. Berlinguette
  • Article |

    The Mackay crystal is a proposed—but synthetically unachieved—nanocarbon molecule that is anticipated to have many desirable properties. Now, a strategy based on annulative coupling of chlorophenanthrene derivatives is reported, allowing streamlined access to an important substructure.

    • Satoshi Matsubara
    • , Yoshito Koga
    • , Yasutomo Segawa
    • , Kei Murakami
    •  & Kenichiro Itami
  • Article |

    Isolating the role of water in aqueous reactions where it is directly involved as a reactant is equally important and challenging. Now, by confining water inside an organic liquid matrix, the authors observe the formation of aqueous-rich nanodomains and find that the reactivity of the system varies with their nanostructure.

    • Nicolas Dubouis
    • , Alessandra Serva
    • , Roxanne Berthin
    • , Guillaume Jeanmairet
    • , Benjamin Porcheron
    • , Elodie Salager
    • , Mathieu Salanne
    •  & Alexis Grimaud
  • News & Views |

    Polyketide synthases are multi-domain enzymes that catalyse the construction of many bioactive natural products. Now, some of the inefficiencies and limitations of these systems have been solved by designing an artificial pathway for carbon–carbon bond formation via iterative rounds of non-decarboxylative thio-Claisen reactions.

    • Anuran K. Gayen
    • , Lindsay Nichols
    •  & Gavin J. Williams
  • Article |

    Computational chemistry has remained largely inaccessible to the experimental chemistry community. Here we report the VIRTUAL CHEMIST, a software suite free for academic use, that enables organic chemists without expertise in computational chemistry to perform virtual screening experiments for asymmetric catalyst discovery and design.

    • Mihai Burai Patrascu
    • , Joshua Pottel
    • , Sharon Pinus
    • , Michelle Bezanson
    • , Per-Ola Norrby
    •  & Nicolas Moitessier
  • Article |

    The Sonogashira cross-coupling is a key strategy in modern synthesis for C–C bond formation and introduction of the versatile alkyne functionality into organic molecules. Now, a complementary method is reported based on the palladium-catalysed cross-coupling of lithium acetylides with aryl bromides.

    • Hugo Helbert
    • , Paco Visser
    • , Johannes G. H. Hermens
    • , Jeffrey Buter
    •  & Ben L. Feringa
  • Article |

    Alkali metals have been traditionally used to promote heterogeneous catalysts, albeit their mode of action remains controversial. Now, the authors demonstrate the multifaceted role of sodium ions in promoting atomically dispersed Ru(iii) on Al2O3, resulting in a superior hydrogenation catalyst.

    • Ruixuan Qin
    • , Lingyun Zhou
    • , Pengxin Liu
    • , Yue Gong
    • , Kunlong Liu
    • , Chaofa Xu
    • , Yun Zhao
    • , Lin Gu
    • , Gang Fu
    •  & Nanfeng Zheng
  • Article |

    The stability of polymer electrolyte membrane fuel cells is limited by the degradation of the cathode catalyst during repetitive start-up/shut-down events — a parasitic oxygen reduction reaction on the anode causes an instantaneous potential jump at the cathode. The issue is now addressed by selectively suppressing the oxygen reduction reaction on the anode by exploiting the metal–insulator transition behaviour of Pt/HxWO3 catalysts.

    • Sang-Mun Jung
    • , Su-Won Yun
    • , Jun-Hyuk Kim
    • , Sang-Hoon You
    • , Jinheon Park
    • , Seonggyu Lee
    • , Seo Hyoung Chang
    • , Seung Chul Chae
    • , Sang Hoon Joo
    • , Yousung Jung
    • , Jinwoo Lee
    • , Junwoo Son
    • , Joshua Snyder
    • , Vojislav Stamenkovic
    • , Nenad M. Markovic
    •  & Yong-Tae Kim
  • Article |

    Unlike with inorganic photocatalysts, the facet-dependent reactivity of conjugated polymers remains elusive. Now, the authors provide molecular-level insights on the reactive facets of crystalline poly(triazine imide) intercalated with LiCl and achieve a remarkable improvement in its overall photocatalytic water splitting activity.

    • Lihua Lin
    • , Zhiyou Lin
    • , Jian Zhang
    • , Xu Cai
    • , Wei Lin
    • , Zhiyang Yu
    •  & Xinchen Wang
  • Article |

    In the development of chemical complexity—and the transition into biology—developing catalytic functionality is essential. Here the authors report the emergence of catalytic activity for two separate reactions (including one demonstrating a positive feedback on replication) in a self-replicating system.

    • Jim Ottelé
    • , Andreas S. Hussain
    • , Clemens Mayer
    •  & Sijbren Otto
  • Article |

    Achieving high enantioselective control in the hydrogenation of aliphatic ketones is a long-standing challenge. Now, the design of a spiro iridium catalyst with a narrow, crowded chiral pocket allows highly enantioselective hydrogenation of these compounds.

    • Feng-Hua Zhang
    • , Fa-Jian Zhang
    • , Mao-Lin Li
    • , Jian-Hua Xie
    •  & Qi-Lin Zhou
  • Article |

    Tuning the structures of subnanometric metal clusters is challenging but can unlock unexpected catalytic properties. Here, the authors show that changing the composition of MFI zeolite-encapsulated PtSn subnanometric clusters by adding just a few tin atoms can lead to a remarkable stability enhancement in propane dehydrogenation.

    • Lichen Liu
    • , Miguel Lopez-Haro
    • , Christian W. Lopes
    • , Sergio Rojas-Buzo
    • , Patricia Concepcion
    • , Ramón Manzorro
    • , Laura Simonelli
    • , Aaron Sattler
    • , Pedro Serna
    • , Jose J. Calvino
    •  & Avelino Corma
  • News & Views |

    Macrocyclic peptide natural products are important medicinal compounds. The catalytic properties of an unusual peptide cyclase enzyme have recently been described — providing opportunities for the engineering and synthesis of structurally complex peptides with novel biological activities.

    • Mohamed A. Attia
    •  & Christopher J. Thibodeaux
  • Editorial |

    Reporting data according to standards accepted by the community is fundamental to the progress of science. In the broad area of catalysis, best practice principles are well consolidated in some subfields, but they are still developing in others.

  • News & Views |

    Catalysts are the heart of CO2 electroreduction technology. Now, a catalyst has been developed that converts CO2 into C2+ products with very high selectivity, stability, and energy efficiency at industrially relevant current densities.

    • Cao-Thang Dinh
  • Article |

    Spinel oxides have attracted interest as water oxidation catalysts due to their efficiency and cost-effectiveness. Now, the covalency competition between tetrahedral and octahedral sites is shown to dominate the OER activity on spinel oxides, and the design principle is used to predict and confirm the superior activity of [Mn]T[Al0.5Mn1.5]OO4.

    • Yuanmiao Sun
    • , Hanbin Liao
    • , Jiarui Wang
    • , Bo Chen
    • , Shengnan Sun
    • , Samuel Jun Hoong Ong
    • , Shibo Xi
    • , Caozheng Diao
    • , Yonghua Du
    • , Jia-Ou Wang
    • , Mark B. H. Breese
    • , Shuzhou Li
    • , Hua Zhang
    •  & Zhichuan J. Xu
  • Article |

    Site-selective functionalization at chemically inert positions within hydrocarbon molecules is a major challenge in organic chemistry. Iron-catalysed borylation at less-reactive positions vicinal to common functional units by sequential isomerization/protoboration of alkenes is reported.

    • Xiaolong Yu
    • , Haonan Zhao
    • , Shibo Xi
    • , Zhongxin Chen
    • , Xiaowei Wang
    • , Lin Wang
    • , Leroy Qi Hao Lin
    • , Kian Ping Loh
    •  & Ming Joo Koh
  • Article |

    The cleavage of C–F bonds through hydrodefluorination is challenging and has been traditionally limited to unsaturated fluorocarbons. Now, a simple plasmonic approach based on the use of aluminium nanocrystal-supported palladium nanoparticles is introduced to effectively upgrade fluoromethane under visible light.

    • Hossein Robatjazi
    • , Junwei Lucas Bao
    • , Ming Zhang
    • , Linan Zhou
    • , Phillip Christopher
    • , Emily A. Carter
    • , Peter Nordlander
    •  & Naomi J. Halas
  • Article |

    The asymmetric O-alkylation of alcohols is a useful route to chiral ethers, but aliphatic secondary alcohols have proven to be difficult substrates. Here the authors report a method to achieve this by developing conditions to avoid the decomposition of the alkylating agent.

    • Ren-Zhe Li
    • , Da-Qi Liu
    •  & Dawen Niu
  • News & Views |

    A rapid and efficient electrochemical reaction requires active catalytic material, as well as proper electrode and cell design. Now, a gas diffusion electrode based on a stainless steel cloth successfully overcomes gas transport limitations for high-current ammonia electrosynthesis in non-aqueous solvents at ambient conditions.

    • Claudio Ampelli
  • Article |

    Methods for the enantioconvergent tertiary C–H functionalization are scarce, but desired for the construction of valuable compounds. Now, a highly enantioconvergent tertiary β-C(sp3)–H amination of racemic ketones with copper/chiral phosphoric acid dual catalysis is reported.

    • Chang-Jiang Yang
    • , Chi Zhang
    • , Qiang-Shuai Gu
    • , Jia-Heng Fang
    • , Xiao-Long Su
    • , Liu Ye
    • , Yan Sun
    • , Yu Tian
    • , Zhong-Liang Li
    •  & Xin-Yuan Liu