Perspective
|
Open Access
Featured
-
-
Article
| Open Access
Efficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions
The conversion of atmospheric N2 into NH3 under ambient pressure is highly interesting but very challenging. In this study, the authors present a tandem air-NOx and NOx-NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx−reduction, resulting in a high NH3 yield from N2 under ambient pressure conditions.
- Wei Liu
- , Mengyang Xia
- & Guidong Yang
-
Article
| Open Access
An isolable, chelating bis[cyclic (alkyl)(amino)carbene] stabilizes a strongly bent, dicoordinate Ni(0) complex
Notwithstanding their success as strongly σ-donating and π-accepting ligands, to date no chelating bis[cyclic (alkyl)(amino)carbenes] have been reported. Here the authors describe a chelating, C2-symmetric bis[cyclic (alkyl)(amino)carbene] ligand, as well as its pseudotetrahedral complexes with iron, cobalt, nickel, and zinc dihalides.
- Braulio M. Puerta Lombardi
- , Morgan R. Faas
- & Roland Roesler
-
Article
| Open Access
Noncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation
Exploitation of noncovalent interactions has received much attention for the design of metal catalysts. However, because of the weak nature, CH-π interactions have been less utilized for the control of organic reactions. Here, the authors report that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes.
- Yushu Jin
- , Boobalan Ramadoss
- & Laurean Ilies
-
Article
| Open Access
Thermally stable Ni foam-supported inverse CeAlOx/Ni ensemble as an active structured catalyst for CO2 hydrogenation to methane
An inverse CeAlOx/Ni/Ni-foam structured catalyst with high thermal stability and water resistance is shown to be effective at CO2 methanation across a wide temperature range because of efficient heat/mass transport.
- Xin Tang
- , Chuqiao Song
- & Lili Lin
-
Article
| Open Access
Tumor-activated in situ synthesis of single-atom catalysts for O2-independent photodynamic therapy based on water-splitting
The utility of single-atom catalysts (SACs) for photodynamic therapy (PDT) has been limited by tumor hypoxia and side effects on normal tissues. Here the authors address these issues by developing an approach of tumor microenvironment-activated in situ synthesis of SACs for tumor-specific water-based PDT.
- Yiyan Yin
- , Xiyang Ge
- & Na Na
-
Article
| Open Access
Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals
C-oligosaccharides are found in natural products and drug molecules, but their synthesis is challenging. Here, the authors report a strategy for the stereoselective and efficient synthesis of Coligosaccharides via palladium-catalyzed nondirected C1–H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors.
- Ya-Nan Ding
- , Mei-Ze Xu
- & Yong-Min Liang
-
Article
| Open Access
Metal free cross-dehydrogenative N-N coupling of primary amides with Lewis basic amines
While the homo N-N coupling of two NH moieties to form the hydrazide N-N bond is well developed, the crossdehydrogenative hetero N-N coupling remains unevolved. Here the authors present an efficient, PhI(OAc)2-mediated intermolecular N-N cross-coupling of primary benzamides with primary and secondary amines.
- Subban Kathiravan
- , Prakriti Dhillon
- & Ian A. Nicholls
-
Article
| Open Access
Keto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water
Hydrogen peroxide photosynthesis is an important reaction that suffers from poor activity due to the high energy barrier of hydrogen extraction in water. Here, we report a keto-form anthraquinone framework that shows promising performance in alkaline conditions.
- Xiangcheng Zhang
- , Silian Cheng
- & Lizhi Zhang
-
Article
| Open Access
Water-participated mild oxidation of ethane to acetaldehyde
The direct conversion of low alkane-like ethane into high-value chemicals has posed a significant challenge. Herein, the authors successfully accomplish a one-step conversion of ethane to C2 oxygenates using a Rh single-atom catalyst under mild conditions.
- Bin Li
- , Jiali Mu
- & Yunjie Ding
-
Article
| Open Access
Single-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis
In addition to maximizing atomic utilization, single-atom catalysts with defined structures can be used to investigate catalytic mechanisms and structure-activity relationships. Here, authors study a non-thermodynamically stable Pt-N2 active site for the electrochemical hydrogen evolution reaction.
- Ziqi Zhang
- , Zhe Zhang
- & Shouhua Feng
-
Article
| Open Access
Wood-inspired metamaterial catalyst for robust and high-throughput water purification
Continuous industrialization and human activities have led to severe water quality deterioration. Here, a structure-function integrated system is developed by Douglas fir wood inspired metamaterial catalysts with robust and high throughput water purification performances.
- Lei Zhang
- , Hanwen Liu
- & Jian Lu
-
Article
| Open Access
Identification of a potent palladium-aryldiphosphine catalytic system for high-performance carbonylation of alkenes
The development of stable and efficient ligands is of vital significance to enhance the catalytic performance of carbonylation reactions of alkenes. Here, the authors develop an aryldiphosphine ligand, used in palladium-catalyzed regioselective carbonylation of alkenes, exhibiting high catalytic performance and strong oxygen-resistance stability.
- Kang Zhao
- , Hongli Wang
- & Feng Shi
-
Article
| Open Access
Silver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones
Epoxides are prominent small-ring O-heterocycles found in a variety of bioactive natural products and pharmaceuticals. Here, the authors report a silver carbene strategy to achieve O-to-C atom exchange of epoxides in a single step, affording diverse fluoroalkylcyclopropanes.
- Linxuan Li
- , Paramasivam Sivaguru
- & Xihe Bi
-
Article
| Open Access
Dioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation
The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.
- Jialiang Wei
- , Junhong Meng
- & Ning Jiao
-
Article
| Open Access
Zirconium and hafnium catalyzed C–C single bond hydroboration
Selective cleavage and subsequent functionalization of C−C single bonds present a fundamental challenge, and the use of inexpensive and Earth-abundant group IV metals for catalytic C−C single-bond cleavage is largely underdeveloped. Here, the authors report zirconium-catalyzed C−C single-bond cleavage and subsequent hydroboration reactions.
- Sida Li
- , Haijun Jiao
- & Lipeng Wu
-
Article
| Open Access
Tuning light-driven oxidation of styrene inside water-soluble nanocages
Selective functionalization of C(sp2)–H bonds under ambient conditions is a persistent synthetic challenge in organic chemistry. Here the authors combine host-guest charge-transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration.
- Souvik Ghosal
- , Ankita Das
- & Jyotishman Dasgupta
-
Article
| Open Access
Remote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins
The synthesis of highly substituted olefins has been pursued for decades. Here, the authors show a carbonyl-directed sequential Heck/isomerization/C–H arylation of alkenes for modular synthesis of stereodefined all-carbon tetrasubstituted olefins.
- Runze Luan
- , Ping Lin
- & Weiping Su
-
Article
| Open Access
Cooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline
The oxidative intermolecular amination of C-H bonds represents a straightforward method to construct aliphatic allylic amines. However, the utilization of widely available internal alkenes remains a synthetic challenge. Here, the authors present a regioselective Cu-catalyzed oxidative allylic C-H amination of internal olefins with azodiformates.
- Le Wang
- , Cheng-Long Wang
- & Shu-Yu Zhang
-
Article
| Open Access
Accessing ladder-shape azetidine-fused indoline pentacycles through intermolecular regiodivergent aza-Paternò–Büchi reactions
Conformationally rigid 3D molecules are of high interest. Here the authors develop intermolecular aza-Paternò-Büchi reactions to access ladder-shape azetidine-fused indoline pentacycles with excellent regiodivergency and stereoselectivity.
- Jianjian Huang
- , Tai-Ping Zhou
- & Fangrui Zhong
-
Article
| Open Access
A nonmetallic plasmonic catalyst for photothermal CO2 flow conversion with high activity, selectivity and durability
In this work, the authors design a Mo2N/MoO2-x nonmetallic plasmonic catalyst by regulating synergy between two specific active sites. Highly efficient, selective, and durable CO2 hydrogenation under relatively mild reaction conditions is achieved
- Xueying Wan
- , Yifan Li
- & Yujie Xiong
-
Article
| Open Access
Mediating trade-off between activity and selectivity in alkynes semi-hydrogenation via a hydrophilic polar layer
The semi-hydrogenation of alkynes faces the trade-off between activity and selectivity due to undesirable over-hydrogenation. Here the authors report an efficient additive-free WO3-based single-atom Pd catalytic system with a vertical size effect of hydrogen spillover to mediate the trade-off between activity and selectivity.
- Jinqi Xiong
- , Shanjun Mao
- & Yong Wang
-
Article
| Open Access
Distribution of Pt single atom coordination environments on anatase TiO2 supports controls reactivity
Elucidating structure-function relationships is crucial for developing efficient catalysts. Here, the authors elucidate Pt single atom coordination environments on anatase TiO2 and correlate active site structure with CO oxidation activity.
- Wenjie Zang
- , Jaeha Lee
- & Xiaoqing Pan
-
Article
| Open Access
Enabling direct-growth route for highly efficient ethanol upgrading to long-chain alcohols in aqueous phase
Achieving efficient carbon chain propagation remains a grand challenge for ethanol upgrading. Here, the authors report sulfur doped Ni@C-Sx catalysts with controllably exposed nickel sites that can dramatically improve direct-growth probability towards long-chain alcohols production.
- Juwen Gu
- , Wanbing Gong
- & Yujie Xiong
-
Article
| Open Access
Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
Ligands capable of accelerating and inducing enantioselectivity in C–H activations with base metal catalysts have remained elusive. Here, the authors report a ligand-accelerated enantioselective C–H alknylation, using a chiral BINOL ligand with a copper catalyst.
- Xin Kuang
- , Jian-Jun Li
- & Jin-Quan Yu
-
Article
| Open Access
Ultrathin covalent organic overlayers on metal nanocrystals for highly selective plasmonic photocatalysis
Controlling molecular interactions on metal surfaces for selective chemical synthesis remains difficult to achieve. Here, we report thin, porous covalent organic overlayers on metal nanocrystals to improve selectivity through plasmonic activation.
- Anubhab Acharya
- , Trimbak Baliram Mete
- & In Su Lee
-
Article
| Open Access
Ultra-high-throughput mapping of the chemical space of asymmetric catalysis enables accelerated reaction discovery
The discovery of highly enantioselective catalysts is challenging due to the complex multidimensional chemical space of asymmetric catalysis and inefficient screening methods. Here, the authors report a general strategy for ultra-high-throughput mapping of the chemical space of asymmetric catalysis with a combination of ion mobility-mass spectrometry and a diastereoisomerization strategy and identify enantioselective primary amine organocatalysts using this method.
- Wenjing Nie
- , Qiongqiong Wan
- & Suming Chen
-
Article
| Open Access
Hydrolase mimic via second coordination sphere engineering in metal-organic frameworks for environmental remediation
Enzymatic degradation of pollutants under mild conditions is promising for efficient degradation of environmental contaminants under facile operation conditions, but natural enzymes tend to lose enzymatic activity in environmental application scenarios. Here, the authors report a metal-organic frameworks-based artificial enzyme system to achieve high hydrolytic activity under mild conditions.
- Xin Yuan
- , Xiaoling Wu
- & Wenyong Lou
-
Article
| Open Access
Self-adaptive amorphous CoOxCly electrocatalyst for sustainable chlorine evolution in acidic brine
Achieving stable and selective chlorine production is of high interest yet challenging. Here the authors report an amorphous CoOxCly catalyst prepared by in situ electrodeposition in acidic saline electrolyte which shows ~100% chlorine evolution selectivity with low overpotential and high stability over 500 h.
- Mengjun Xiao
- , Qianbao Wu
- & Chunhua Cui
-
Article
| Open Access
Divergent access to 5,6,7-perifused cycles
The lack of efficient and diverse synthesis strategy has hindered the study of perifused cycles. Here, the authors report a metal-catalyzed cascade electrocyclization to access 5,6,7-perifused cycles, and demonstrated the versatility of this protocol in the late-stage modification of pharmaceuticals.
- Jingpeng Han
- , Yongjian Yang
- & Baosheng Li
-
Article
| Open Access
Sustainable production of dopamine hydrochloride from softwood lignin
Efficient production of dopamine direct from lignin is a highly desirable target but extremely challenging. Here, we report an innovative strategy for the sustainable production of dopamine hydrochloride from softwood lignin with a mass yield of 6.4 wt.%.
- Lin Dong
- , Yanqin Wang
- & Zupeng Chen
-
Article
| Open Access
Constructing multiple active sites in iron oxide catalysts for improving carbonylation reactions
Surface engineering of Fe sites was used to improve the carbonylation reaction of aryl halides and amines/alcohols with CO. The elementary steps of phenyl iodide activation, CO insertion and C-N/C-O coupling were catalyzed respectively, leading to improved catalytic activity.
- Shujuan Liu
- , Teng Li
- & Xinjiang Cui
-
Comment
| Open Access
Direct synthesis of urea from carbon dioxide and ammonia
Urea, a crucial nitrogen fertilizer, plays a vital role in meeting global food demand. However, its current production method is energy-intensive and environmentally unfriendly. In this commentary article, the authors propose strategies to address and overcome these challenges.
- Jie Ding
- , Runping Ye
- & Maohong Fan
-
Article
| Open Access
Fluorocarbonylation via palladium/phosphine synergistic catalysis
Despite the growing importance of fluorinated organic compounds introduction of fluorine into organic molecules is still challenging. Here, the authors present the development of palladium and phosphine synergistic redox catalysis of fluorocarbonylation of potassium aryl/alkyl trifluoroborate.
- Mingxin Zhao
- , Miao Chen
- & Pingping Tang
-
Article
| Open Access
Spin selection in atomic-level chiral metal oxide for photocatalysis
The spin degree of freedom is a key intrinsic parameter for carrier dynamics and surface reaction kinetics in photocatalysis. Here, the authors report a chiral zinc oxide with spin selectivity effect. It can effectively induce spin polarization, thereby promoting electron spin-related redox catalysis.
- Minhua Ai
- , Lun Pan
- & Ji-Jun Zou
-
Article
| Open Access
Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands
Noble metals have been extensively employed in a variety of hydrotreating catalyst systems. Here, the authors demonstrate that coordinating Pd with alkenyl-type ligands creates an electron-rich environment for Pd entity to weaken the interaction between Pd and unsaturated C for selective hydrogenation.
- Jianghao Zhang
- , Wenda Hu
- & Yong Wang
-
Article
| Open Access
A 13-million turnover-number anionic Ir-catalyst for a selective industrial route to chiral nicotine
The development of catalysts for practical asymmetric hydrogenation of ketones remains an important goal of synthetic organic chemistry. Here, an anionic iridium catalyst with excellent activity is reported and used in a hundred-kilogram-scale reduction as part of a route to chiral nicotine.
- Congcong Yin
- , Ya-Fei Jiang
- & Xumu Zhang
-
Article
| Open Access
Chemoselectivity change in catalytic hydrogenolysis enabling urea-reduction to formamide/amine over more reactive carbonyl compounds
The selective transformation of a less reactive carbonyl moiety in the presence of more reactive ones can realize straightforward and environmentally benign chemical processes but such a transformation is highly challenging. Here, the authors report an Ir catalyst for the selective hydrogenolysis of urea derivatives, which are the least reactive carbonyl compounds, affording formamides and amines even in the presence of more reactive carbonyl groups such as ester.
- Takanori Iwasaki
- , Kazuki Tsuge
- & Kyoko Nozaki
-
Article
| Open Access
Palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides
Acid chloride formation is generally limited to the chlorination of carboxylic acids. Here, the authors report a palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for the synthesis of various alkyl acid chlorides.
- Fei Wu
- , Bo Wang
- & Zheng-Hui Guan
-
Article
| Open Access
Computation-based regulation of excitonic effects in donor-acceptor covalent organic frameworks for enhanced photocatalysis
The donor-acceptor (D-A) interaction and exciton binding energy have been investigated for a series of D-A pairs by DFT calculations. Here, the authors synthesize the corresponding D-A COFs, and demonstrate that their photocatalytic hydrogen production activities match well with the calculation results.
- Yunyang Qian
- , Yulan Han
- & Hai-Long Jiang
-
Article
| Open Access
Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis
The cleavage and functionalization of C-S bonds has become a hot topic. Here the authors report a novel and efficient protocol that enables direct oxidative cleavage and ammoxidation of organosulfur compounds by heterogeneous nonprecious-metal Co-N-C catalyst comprising graphene encapsulated Co nanoparticles and Co-Nx sites.
- Huihui Luo
- , Shuainan Tian
- & Wen Dai
-
Article
| Open Access
Direct allylic acylation via cross-coupling involving cooperative N‑heterocyclic carbene, hydrogen atom transfer, and photoredox catalysis
The versatility and importance of β,γ-unsaturated ketones has been appreciated for a long time in synthesis and medicinal chemistry. Here, the authors use carboxylic acids and readily available olefins as substrates for transformations involving N‑heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for the synthesis of β,γ-unsaturated ketones.
- Xiaochen Wang
- , Rongxin Yang
- & Qingmin Wang
-
Article
| Open Access
Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation
Single-site pincer-ligated iridium complexes exhibit the ability for C-H activation but suffer from instability and difficulty in catalyst recycling. Here the authors design an atomically dispersed Ir catalyst which can be considered the bridge between homogeneous and heterogeneous catalysis and displays an outstanding catalytic performance in n-butane dehydrogenation.
- Xiaowen Chen
- , Xuetao Qin
- & Ding Ma
-
Article
| Open Access
Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson’s catalyst for hydroformylation of olefins
Heterogeneous catalysts for olefin hydroformylation are highly desired but suffer from poor activity. Herein, the authors report that rhodium nanoparticles supported on siliceous MFI zeolite with abundant silanol nests are very active for hydroformylation, affording a turnover frequency that outperforms the classical Wilkinson’s catalyst.
- Yifeng Liu
- , Zhiqiang Liu
- & Feng-Shou Xiao
-
Article
| Open Access
Photocatalytic CO2 reduction using La-Ni bimetallic sites within a covalent organic framework
A bifunctional dual-atom photocatalysts with La and Ni sites is shown to be have efficient generation and transfer of photocarriers from the optically active La center to the catalytically active Ni center for promoting efficient CO2 reduction to CO.
- Min Zhou
- , Zhiqing Wang
- & Yueli Liu
-
Article
| Open Access
Regulating the electronic structure through charge redistribution in dense single-atom catalysts for enhanced alkene epoxidation
The interaction among single sites in densely populated single-atom catalysts (SACs) has received much attention. Here the authors report a general and facile strategy for the synthesis of several densely populated SACs and decipher the influence of density on regulating their electronic structure and catalytic performance in alkene epoxidation.
- Hongqiang Jin
- , Kaixin Zhou
- & Changyan Cao
-
Article
| Open Access
Achieving volatile potassium promoted ammonia synthesis via mechanochemistry
Potassium oxide is used as a promotor in industrial ammonia synthesis, although metallic potassium is better in theory. Here, the authors demonstrate metallic potassium, an unstable metal that easily volatilizes at high temperature, can be used as a promotor for ammonia synthesis.
- Jong-Hoon Kim
- , Tian-Yi Dai
- & Jong-Beom Baek
-
Article
| Open Access
Electrochemical generation of hydrogen peroxide from a zinc gallium oxide anode with dual active sites
Developing efficient anodes for H2O2 production via water oxidation remains challenging. Here, the authors report a ZnGa2O4 anode with dual active sites to improve the selectivity and to resist the decomposition of H2O2, and the peak faradaic efficiency reaches 82% at a low potential.
- Lejing Li
- , Zhuofeng Hu
- & Jimmy C. Yu
-
Article
| Open Access
Direct synthesis of extra-heavy olefins from carbon monoxide and water
Fischer-Tropsch synthesis is challenged by the trade-off between enhancing C-C coupling and suppressing further hydrogenation of olefins. Here the authors break this challenge by developing a universal strategy to synthesis extra-heavy olefins from carbon monoxide and water via the sustained release of hydrogen and selective extraction of olefins.
- Chuanhao Wang
- , Junjie Du
- & Jie Zeng
-
Article
| Open Access
Interfacial assembly of binary atomic metal-Nx sites for high-performance energy devices
An interfacial assembly strategy was developed to construct single-atom binary Fe/Co-Nx sites with a high accessible site density of 7.6 × 1019 sites per gram which results in increased power densities in fuel cells and Zn/air batteries.
- Zhe Jiang
- , Xuerui Liu
- & Jin-Song Hu
Emerging trends in chiral inorganic nanomaterials for enantioselective catalysis