B18-Core EXAFS
I11-High Resolution Powder Diffraction
|
Shan
Dai
,
Xiangdi
Zeng
,
Benjamin J.
Moore
,
Yuxiang
Zhu
,
Yuhang
Yang
,
Zi
Wang
,
Luyan
Li
,
Te
Wang
,
Ivan
Da Silva
,
Luke
Keenan
,
Floriana
Tuna
,
Daniel
Lee
,
Sarah
Day
,
Lucy
Saunders
,
Martin
Schroeder
,
Sihai
Yang
Abstract: Metal–organic framework (MOF) materials share some common features with metalloenzymes including site-isolated metal centers that template dynamic substrate activation within a functionalized cavity or pocket. We report the light-induced reversible binding of CO2 in a cerium-based MOF, Ce-UiO-66-NH2, incorporating an amino functionalized linker, which enables photoreduction of CO2 to CO in H2O without using sacrificial agents. A production rate for CO of 126 μmol·g–1·h–1 with 100% selectivity is observed, outperforming its non-amine analogue (Ce-UiO-66) and benchmark catalysts reported to date. In situ infrared, X-ray absorption, electron paramagnetic resonance and transient absorption spectroscopy reveal that photoexcitation induces a ligand-to-metal charge transfer to generate transient open Ce(III) sites that bind CO2 in a μ-(η1-O)(η1-C) binding mode. This binding is reversible and activates CO2 for subsequent photoreduction to CO. This work will promote the design of photocatalysts capable of synthesizing fuels from CO2.
|
Mar 2026
|
|
B18-Core EXAFS
I11-High Resolution Powder Diffraction
|
Zhaodong
Zhu
,
Xin
Lian
,
Xue
Han
,
Zi
Wang
,
Siyu
Zhou
,
Meng
He
,
Tianze
Zhou
,
Yuting
Chen
,
Mengtian
Fan
,
Wenyuan
Huang
,
Yuhang
Yang
,
Shaojun
Xu
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Jeff
Armstrong
,
Svemir
Rudic
,
William
Thornley
,
Evan
Tillotson
,
Daniel
Lee
,
Sarah
Haigh
,
Shiyu
Fu
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sihai
Yang
Diamond Proposal Number(s):
[37887, 31729, 36450]
Abstract: Catalytic hydrodeoxygenation (HDO) is critical for bio-oil upgrading, yet the selective cleavage of stable C(sp2)–OH bonds in lignin-derived substrates under aqueous conditions remains a challenge. Here, we report a heteroatomic zeolite catalyst, RuFA/SAPO-34-Nb, featuring few-atom Ru clusters on a Nb(V)-modified SAPO-34 framework, which achieves highly efficient HDO of lignin-derived creosol (2-methoxy-4-methylphenol) in water. Under mild conditions (250 °C, 7 bar H2, 24 h), this catalyst delivers quantitative conversion of creosol to toluene (99.2% conversion, 99.6% selectivity), fully preserving the aromaticity of lignin-derived feedstocks─a key requirement for sustainable production of chemicals. Synchrotron X-ray diffraction, X-ray absorption spectroscopy, and inelastic neutron scattering, combined with theoretical modeling, elucidate the cooperative mechanism: the Nb(V) sites selectively cleave the strong C–O bonds, while the few-atom Ru cluster generates hydrogen species with an exceptionally low rotational barrier of 65 cm–1. This synergistic interaction enables the direct and selective HDO of C(sp2)–O bonds without saturation of the aromatic ring. This work establishes a promissing strategy for aqueous-phase HDO catalysis and provides a general approach for designing bimetallic zeolite catalysts to convert lignin-derived compounds to value-added aromatic chemicals, advancing sustainable biorefinery processes.
|
Jan 2026
|
|
B18-Core EXAFS
|
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.
|
Nov 2025
|
|
I19-Small Molecule Single Crystal Diffraction
|
Thien D.
Duong
,
Jiangnan
Li
,
Ruohan
Li
,
Xin
Lian
,
Yinlin
Chen
,
Jiarui
Fan
,
Joseph
Hurd
,
Lixia
Guo
,
Daniel
Lee
,
Mark
Warren
,
Sihai
Yang
Diamond Proposal Number(s):
[41123]
Abstract: The capture of xenon (Xe) and krypton (Kr) from the off-gas of used nuclear fuel is of great importance to the treatment of radioactive wastes and production of high purity Xe. Solid sorbents, in particular metal–organic frameworks (MOFs), show promise in gas capture. However, the unknown radiation resistance of MOFs has limited their development. Herein, the efficient capture and separation of Xe/Kr by MFM-520, which strikes a remarkable stability toward 1750 kilogray (kGy) γ-irradiation, is reported. Under ambient conditions, dynamic breakthrough experiments confirm the efficient separation performance, yielding a Xe capacity of 66 and 0.2 mg g−1 from a by-product of air separation (Xe/Kr: 20/80; v/v) and off-gas (Xe/Kr: 400/40 ppm balance in air), respectively. In situ synchrotron X-ray single crystal diffraction and solid-state nuclear magnetic resonance (ssNMR) studies reveal that the optimal micropore of MFM-520 underpins specific host-guest interactions to Xe, resulting in selective Xe capture.
|
Oct 2025
|
|
B18-Core EXAFS
I20-EDE-Energy Dispersive EXAFS (EDE)
|
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.
|
Oct 2025
|
|
I11-High Resolution Powder Diffraction
|
Lutong
Shan
,
Tianxiang
Chen
,
Shiyun
Li
,
Boya
Tang
,
Yuhang
Yang
,
Peng
Rao
,
Jiangnan
Li
,
Ching Kit Tommy
Wun
,
Daniel
Lee
,
Mufan
Li
,
Tsz Woon Benedict
Lo
,
Sihai
Yang
Diamond Proposal Number(s):
[37887]
Abstract: The concerted electron–proton transfer (CEPT) can substantially enhance the microkinetics of electrocatalysis by circumventing the formation of high-energy intermediates. Herein, we report the decoration of the MFI zeolite matrix with isolated Cu(II) sites in the proximity of intrinsic Brønsted acid sites (BASs), promoting the CEPT synergy in electrocatalysis. By modulating the spatial arrangement of “Cu-BAS” pairs in Cu-Z(23) zeolite, we show a Faradaic efficiency of 98% for electroreduction of nitrate to ammonia, achieving an exceptional yield of 103.1 mg h–1 cm–2 at a current density of 1.3 A cm–2. Cu-Z(23) also exhibits an excellent activity at low concentrations of nitrate (e.g., 50 ppm) and a high catalytic stability of 50 h. Synchrotron X-ray powder diffraction, solid-state nuclear magnetic resonance spectroscopy, and modeling studies reveal the critical role of the proximate “Cu-BAS” pairs in facilitating the CEPT process. This approach uncovers the overlooked capability of “electrical insulating” zeolites as effective electrocatalysts to drive future sustainable chemical synthesis.
|
Sep 2025
|
|
B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
|
Boya
Tang
,
David
Brooks
,
Meng
He
,
Yinlin
Chen
,
Zhaozhao
Hu
,
Xue
Han
,
Jiangnan
Li
,
Siyu
Zhao
,
Jiarui
Fan
,
Yukun
Ye
,
Ivan
Da Silva
,
Cheng
Li
,
Zi
Wang
,
Lutong
Shan
,
Bing
Han
,
Weiyao
Li
,
Daniil
Polyukhov
,
Bing
An
,
Catherine
Dejoie
,
Martin
Wilding
,
Shaojun
Xu
,
Meredydd
Kippax-Jones
,
Zhaodong
Zhu
,
Yujie
Ma
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Mark D.
Frogley
,
Louise S.
Natrajan
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[37900, 37887, 36450]
Abstract: Photocatalytic synthesis of hydrogen peroxide (H2O2) from oxygen (O2) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H2L1) with a [(H2L2)ReI(CO)3Cl] (H2L2 = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H2O2 from O2 of 8.50 mmol gcat–1 h–1 and a record turnover frequency (TOF) of 28.7 h–1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [ReI(CO)3Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H2O2 generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.
|
Jul 2025
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
|
Wenling
Zhao
,
Jiangnan
Li
,
Ke
Li
,
Jiapeng
Jiao
,
Shiqiang
Liu
,
Jiahao
Yang
,
Mark D.
Frogley
,
Yaguang
Peng
,
Yiyong
Wang
,
Hengan
Wang
,
Shipeng
Zhang
,
Lihong
Jing
,
Chengcheng
Liu
,
Sihai
Yang
,
Xinchen
Kang
,
Buxing
Han
Abstract: Photoreduction of CO2 is often hindered by the sluggish kinetics for its activation. Refinement of host–guest interactions is an effective strategy to overcome this barrier. Here, we report the immobilization of active Co(II) sites within a covalent-organic framework (COF) with a one-dimensional (1D) chain structure, Co-PyPDA-COF, which demonstrates a remarkable CO generation rate of 30.5 mmol g−1 h−1 and a high CO selectivity of 95.8% in 2 h for CO2 photoreduction at room temperature. The pore size of Co-PyPDA-COF is comparable to the diameter of CO2, which allows simultaneous interaction of a single CO2 molecule with the two Co(II) sites. The enhanced interaction result in increased local CO2 pressure, limited CO2 diffusion after adsorption, shortened distance for photoelectron transfer, and reduced energy barrier for the rate-determining step in CO2 reduction, promoting CO2 activation and conversion. This work opens a new way to design efficient catalysts by optimizing the pore size of the host.
|
Jul 2025
|
|
B18-Core EXAFS
I11-High Resolution Powder Diffraction
|
Xu
Chen
,
Dhruv
Menon
,
Xiaoliang
Wang
,
Meng
He
,
Mohammad Reza
Alizadeh Kiapi
,
Mehrdad
Asgari
,
Yuexi
Lyu
,
Xianhui
Tang
,
Luke L.
Keenan
,
William
Shepard
,
Lik H.
Wee
,
Sihai
Yang
,
Omar K.
Farha
,
David
Fairen-Jimenez
Diamond Proposal Number(s):
[32566, 34552]
Open Access
Abstract: Selective CO2 capture from industry is crucial for reducing emissions from fossil fuel combustion. Flexible metal-organic frameworks (MOFs) have shown promise for CO2 adsorption via differential binding and size-exclusion mechanisms. However, achieving precise pore-size control to selectively capture CO2, particularly in the presence of N2 and water, remains a challenge. Here, we demonstrate a strategy for frustrating framework flexibility in a MOF to create an optimal, confined pore environment that enhances selective CO2 recognition while maintaining high working capacity. We designed a flexible MOF, Cambridge University (CU)-4, by using a bulky cubane-derived ligand and In3+ ions that undergo dynamic breathing with a 2 Å contraction upon solvent exchange and removal. In situ synchrotron X-ray diffraction and molecular simulations reveal that the stable narrow-pore configuration creates a hydrogen-rich cavity that selectively binds CO2 via multiple hydrogen bonds. This physisorption-based CO2 recognition remains effective even at 80% humidity, making CU-4 promising for post-combustion carbon capture.
|
Jan 2025
|
|
B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
|
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.
|
Jan 2025
|
|
