B18-Core EXAFS
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Qingqing
Mei
,
Wenyuan
Huang
,
Longfei
Lin
,
Xue
Han
,
Shaojun
Xu
,
Bing
An
,
Svemir
Rudic
,
Rongsheng
Cai
,
Sarah J.
Haigh
,
Buxing
Han
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[36450]
Open Access
Abstract: The synthesis of organic amines via reductive amination of biomass-derived carbonyl compounds is an important target for sustainable chemical industries. The control of selectivity for the formation of primary amines versus secondary amines is challenging, and high temperature and pressures using H2 are required to generate the desired selectivity. Herein, we report the highly selective reductive amination of a broad range of aldehydes and ketones by NH3 and H2 over Rh/MFM-300(Cr) to form primary amines with a selectivity of up to 99% under ambient conditions. Inelastic neutron scattering reveals that the Rh species not only promote the hydrogenation process, but also catalyzes the ammonolysis of the Schiff base intermediate, facilitating the selective synthesis of primary amines. This protocol achieves selective reductive amination at 25 °C and 1 atm, providing an energy-efficient route to a broad spectrum of amines.
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Nov 2025
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B18-Core EXAFS
I20-EDE-Energy Dispersive EXAFS (EDE)
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Wenyuan
Huang
,
Bing
An
,
Zeyu
Chen
,
Yu
Han
,
Yinlin
Chen
,
Jiangnan
Li
,
Xue
Han
,
Shaojun
Xu
,
Danielle
Crawshaw
,
Evan
Tillotson
,
Sarah J.
Haigh
,
Bing
Han
,
Christopher M. A.
Parlett
,
Luke
Keenan
,
Svemir
Rudic
,
Yongqiang
Cheng
,
Ben F.
Spencer
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[28575, 31729]
Open Access
Abstract: The development of earth-abundant metal-based catalysts is an important goal for the synthesis of fine chemicals. Here, an active nickel catalyst supported on a robust metal–organic framework, MFM-300(Cr), is reported which shows an exceptional performance for reductive amination, a reaction that has long been dominated by noble metals. Ni/MFM-300(Cr) promotes the synthesis of 38 primary amines via reductive amination of their parent carbonyl compounds, including biomass-derived aldehydes and ketones, using NH3 in the presence of H2 operating under relatively mild conditions (5 bar and 160 °C). X-ray absorption spectroscopy confirms the formation of mixtures of metallic Ni0 and Nin+ active sites, while in situ inelastic neutron scattering, coupled with modeling, reveals details of the mechanism of catalysis involving the formation of N-benzyl-1-phenylmethanediamine (BPDI) as an intermediate species in the generation of benzylamine. Cooperativity between Ni sites and MFM-300(Cr) creates an optimal microenvironment for the efficient activation of carbonyl compounds and the selective production of primary amines using a non-precious metal-based catalyst.
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Oct 2025
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B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Zhaodong
Zhu
,
Mengtian
Fan
,
Meng
He
,
Bing
An
,
Yinlin
Chen
,
Shaojun
Xu
,
Tianze
Zhou
,
Alena M.
Sheveleva
,
Meredydd
Kippax-Jones
,
Lutong
Shan
,
Yongqiang
Chen
,
Hamish
Cavaye
,
Jeff
Armstrong
,
Svemir
Rudic
,
Stewart F.
Parker
,
William
Thornley
,
Evan
Tillotson
,
Matthew
Lindley
,
Shenglong
Tian
,
Daniel
Lee
,
Shiyu
Fu
,
Mark D.
Frogley
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sarah J.
Haigh
,
Sihai
Yang
Abstract: The methanol-to-olefins (MTO) process has the potential to bridge future gaps in the supply of sustainable lower olefins. Promoting the selectivity of propylene and ethylene and revealing the catalytic role of active sites are challenging goals in MTO reactions. Here, we report a novel heteroatomic silicoaluminophosphate (SAPO) zeolite, SAPO-34-Ta, which incorporates active tantalum(V) sites within the framework to afford an optimal distribution of acidity. SAPO-34-Ta exhibits a remarkable total selectivity of 85.8% for propylene and ethylene with a high selectivity of 54.9% for propylene on full conversion of methanol at 400 oC. In situ and operando synchrotron powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy and inelastic neutron scattering, coupled with theoretical calculations, reveal trimethyloxonium as the key reaction intermediate, promoting the formation of first carbon-carbon bonds in olefins. The tacit cooperation between tantalum(V) and Brønsted acid sites within SAPO-34 provides an efficient platform for selective production of lower olefins from methanol.
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Jan 2025
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Yu
Han
,
Wenyuan
Huang
,
Meng
He
,
Bing
An
,
Yinlin
Chen
,
Xue
Han
,
Lan
An
,
Meredydd
Kippax-Jones
,
Jiangnan
Li
,
Yuhang
Yang
,
Mark D.
Frogley
,
Cheng
Li
,
Danielle
Crawshaw
,
Pascal
Manuel
,
Svemir
Rudic
,
Yongqiang
Chen
,
Ian
Silverwood
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Ben F.
Spencer
,
Marek
Nikiel
,
Daniel
Lee
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[37155, 36474]
Open Access
Abstract: Capture of trace benzene is an important and challenging task. Metal–organic framework materials are promising sorbents for a variety of gases, but their limited capacity towards benzene at low concentration remains unresolved. Here we report the adsorption of trace benzene by decorating a structural defect in MIL-125-defect with single-atom metal centres to afford MIL-125-X (X = Mn, Fe, Co, Ni, Cu, Zn; MIL-125, Ti8O8(OH)4(BDC)6 where H2BDC is 1,4-benzenedicarboxylic acid). At 298 K, MIL-125-Zn exhibits a benzene uptake of 7.63 mmol g−1 at 1.2 mbar and 5.33 mmol g−1 at 0.12 mbar, and breakthrough experiments confirm the removal of trace benzene (from 5 to <0.5 ppm) from air (up to 111,000 min g−1 of metal–organic framework), even after exposure to moisture. The binding of benzene to the defect and open Zn(II) sites at low pressure has been visualized by diffraction, scattering and spectroscopy. This work highlights the importance of fine-tuning pore chemistry for designing adsorbents for the removal of air pollutants.
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Nov 2024
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Yu
Han
,
David
Brooks
,
Meng
He
,
Yinlin
Chen
,
Wenyuan
Huang
,
Boya
Tang
,
Bing
An
,
Xue
Han
,
Meredydd
Kippax-Jones
,
Mark D.
Frogley
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Svemir
Rudic
,
Yongqiang
Chen
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Catherine
Dejoie
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[33115, 30398]
Open Access
Abstract: The functionalization of metal–organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalized with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g–1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy, and inelastic neutron scattering, coupled with density functional theory modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by −CH···Cl and Cl···π interactions in porous materials.
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Oct 2024
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I11-High Resolution Powder Diffraction
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Xiangdi
Zeng
,
Zi
Wang
,
Meng
He
,
Wanpeng
Lu
,
Wenyuan
Huang
,
Bing
An
,
Jiangnan
Li
,
Mufan
Li
,
Ben F.
Spencer
,
Sarah J.
Day
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[37155]
Open Access
Abstract: Phenylacetylene is a detrimental impurity in the polymerisation of styrene, capable of poisoning catalysts even at ppm levels and significantly degrading the quality of polystyrene. The semi-hydrogenation of phenylacetylene to styrene instead of ethylbenzene is, therefore, an important industrial process. We report a novel cerium(IV)-based metal-organic framework (denoted as Ce-bptc), which is comprised of {Ce6} clusters bridged by biphenyl-3,3’,5,5’-tetracarboxylate linkers. Ce-bptc serves as an ideal support for palladium nanoparticles and the Pd@Ce-bptc catalyst demonstrates an excellent catalytic performance for semi-hydrogenation of phenylacetylene, achieving a selectivity of 93% to styrene on full conversion under ambient conditions with excellent reusability. In situ synchrotron X-ray powder diffraction and electron paramagnetic resonance spectroscopy revealed the binding domain of phenylacetylene within Ce-bptc and details of the reaction mechanism.
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Oct 2024
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
|
Wenyaun
Huang
,
Qingqing
Mei
,
Shaojun
Xu
,
Bing
An
,
Meng
He
,
Jiangnan
Li
,
Yinlin
Chen
,
Xue
Han
,
Tian
Luo
,
Lixia
Guo
,
Joseph
Hurd
,
Daniel
Lee
,
Evan
Tillotson
,
Sarah
Haigh
,
Alex
Walton
,
Sarah
Day
,
Louise S.
Natrjan
,
Martin
Schroeder
,
Sihai
Yang
Open Access
Abstract: Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal-organic framework supported ruthenium catalyst, Ru/MFM-300(Cr). Highly selective production of N-formamides has been observed for a wide range of carbonyl compounds. Synchrotron X-ray powder diffraction reveals the presence of strong host-guest binding interactions via hydrogen bonding and parallel-displaced π···π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.
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Oct 2023
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B18-Core EXAFS
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Yujie
Ma
,
Xue
Han
,
Shaojun
Xu
,
Zhe
Li
,
Wanpeng
Lu
,
Bing
An
,
Daniel
Lee
,
Sarayute
Chansai
,
Alena M.
Sheveleva
,
Zi
Wang
,
Yinlin
Chen
,
Jiangnan
Li
,
Weiyao
Li
,
Rongsheng
Cai
,
Ivan
Da Silva
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Lewis
Hughes
,
Pascal
Manuel
,
Anibal J.
Ramirez-Cuesta
,
Sarah J.
Haigh
,
Christopher
Hardacre
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[19850]
Open Access
Abstract: Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal–organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat–1 h–1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat–1 h–1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe–O(H)–Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe–O(CH3)–Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.
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Sep 2023
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B18-Core EXAFS
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Run
Zou
,
Sarayute
Chansai
,
Shaojun
Xu
,
Bing
An
,
Shima
Zainal
,
Yangtao
Zhou
,
Ruojia
Xin
,
Pan
Gao
,
Guangjin
Hou
,
Carmine
D’agostino
,
Stuart M.
Holmes
,
Christopher
Hardacre
,
Yilai
Jiao
,
Xiaolei
Fan
Diamond Proposal Number(s):
[29271]
Open Access
Abstract: Stabilisation of metal species using hydroxyl-rich dealuminated zeolites is a promising method for catalysis. However, insights into the interactions between the hydroxyl groups in zeolite and noble metals and their effects on catalysis are not yet fully understood. Herein, comparative studies were conducted using Pt catalysts supported on hydroxyl-rich dealuminated Beta (deAl-Beta) and the pristine proton-form Beta (H-Beta) for catalytic oxidation of toluene. The findings suggest that during impregnation the Pt precursor (i.e., Pt(NH3)4(NO3)2) interacted with different sites on deAl-Beta and H-Beta, leading to the formation of supported Pt nanoparticles with different physicochemical properties. The resulting Pt/deAl-Beta exhibited improved activity and anti-coking ability than Pt/H-Beta in catalytic toluene oxidation. According to toluene-TPD, 1H NMR relaxation and in situ DRIFTS characterisation, the enhanced performance of Pt/deAl-Beta could be ascribed to (i) the active Pt-O sites stabilised by hydroxyl groups, which interact with toluene easily for conversion, and (ii) the acid-free feature of the deAl-Beta support, which avoids the formation of coke precursors (such as benzoate species) on the catalyst surface. Findings of the work can serve as the design guidelines for making effective supported metal catalysts using zeolitic carriers.
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Sep 2023
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I20-EDE-Energy Dispersive EXAFS (EDE)
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Mengtian
Fan
,
Shaojun
Xu
,
Bing
An
,
Alena M.
Sheveleva
,
Alexander
Betts
,
Joseph
Hurd
,
Zhaodong
Zhu
,
Meng
He
,
Dinu
Iuga
,
Longfei
Lin
,
Xinchen
Kang
,
Christopher M. A.
Parlett
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Luke L.
Keenan
,
Daniel
Lee
,
Martin P.
Attfield
,
Sihai
Yang
Diamond Proposal Number(s):
[28575]
Open Access
Abstract: The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91%. The incorporation of Al(III) and Nb(V) sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure. Operando X-ray absorption, diffuse reflectance infrared and solid-state NMR spectroscopy collectively reveal the molecular mechanism of the conversion of adsorbed 2-MTHF over AlNb-MCM-41. Specifically, the atomically-dispersed Nb(V) sites play an important role in binding 2-MTHF to drive the conversion. Overall, this study highlights the potential of hetero-atomic mesoporous solids for the manufacture of renewable materials.
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Oct 2022
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