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Instruments / Technical Area	Publication Details	Published
B18-Core EXAFS	Selective reductive amination of carbonyls to primary amines under ambient conditions over Rh/MFM-300(Cr) 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 Angewandte Chemie International Edition DOI: 10.1002/anie.202519641 Diamond Proposal Number(s): [36450] Open Access Show Abstract ▼ 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
B18-Core EXAFS I20-EDE-Energy Dispersive EXAFS (EDE)	Synthesis of primary amines via reductive amination of aldehydes and ketones over a Ni-Doped MFM-300(Cr) catalyst 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 Advanced Science DOI: 10.1002/advs.202508892 Diamond Proposal Number(s): [28575, 31729] Open Access Show Abstract ▼ 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
B18-Core EXAFS B22-Multimode InfraRed imaging And Microspectroscopy I11-High Resolution Powder Diffraction	Photocatalytic synthesis of hydrogen peroxide by rhenium modified metal-organic frameworks incorporating bianthracene ligands 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 Journal Of The American Chemical Society DOI: 10.1021/jacs.5c00603 Diamond Proposal Number(s): [37900, 37887, 36450] Show Abstract ▼ 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
B18-Core EXAFS	Multiscale catalyst design to enhance interfacial hydroxyl anion supply and accelerate water dissociation for neutral oxygen evolution Mei Han , Jieshu Zhou , Shaojun Xu , Honggang Sun , Xin Zi , Ning Wang , Jingrui Han , Weijia Zhou , Haibin Wang , Kangning Liu , Emiliano Cortés , Songhua Chen , Mingchuan Luo , Jieqiong Shan , Min Liu , Ziyun Wang , Hongyan Liang , Yongchang Liu Advanced Functional Materials 14 DOI: 10.1002/adfm.202503470 Diamond Proposal Number(s): [19850] Show Abstract ▼ Abstract: Neutral water electrolysis faces challenges due to insufficient OH− supply, which leads to inefficient oxygen evolution reaction (OER). Constructing a localized OH−-enriched reaction environment is crucial for enhancing the neutral OER activity. Here, an integrated catalyst design aimed at optimizing the local reaction environment is presented to improve catalytic activity. Specifically, a high-curvature needle morphology is constructed to strengthen the local electric field, which induces localized OH− accumulation and mitigates OH− deficiency in the neutral electrolyte. Moreover, implanting Ag cores not only improves the conductivity and long-term stability of the NiCo-based catalytic shells but also enables Ag diffusion to dope the catalytic layer. At the atomic scale, Ag dopants modify the activity of oxygen ligands and the polarity of metal-oxygen (M─O) bonds within the symmetric spinel structure. This modification facilitates surface reconstruction, resulting in the formation of a distorted Ag-O-Ni/Co-OH network. The elongation of the Ni/Co−O bond generates an inhomogeneous charge distribution that optimizes water polarization and deprotonation, accelerating water dissociation and OH formation. The multiscale catalyst design results in a unique interface featuring a high-curvature surface and atomic-scale polarized M─O networks, synergistically enhancing local OH accumulation. Therefore, the optimal Ag@NiCo2O4 catalyst delivers a η10 = 295 mV in an H-cell electrolyzer and 2.1 V @1 A cm−2 in a membrane electrode assembly electrolyzer. This finding provides a practical design for OER electrocatalysts in neutral electrolytes and opens a new avenue for optimizing catalytic performance by integrating multiple strategies.	May 2025
B18-Core EXAFS B22-Multimode InfraRed imaging And Microspectroscopy I11-High Resolution Powder Diffraction	Selective production of olefins from methanol over a heteroatomic SAPO-34 zeolite 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 Science Bulletin 149 DOI: 10.1016/j.scib.2024.12.050 Show Abstract ▼ 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
I11-High Resolution Powder Diffraction	Hierarchical porous metal-organic polyhedra for efficient oxidative cleavage of β-O-4 bonds in lignin model compound Xinchen Kang , Lili Li , Hengan Wang , Tian Luo , Shaojun Xu , Yinlin Chen , Joseph H. Carter , Zi Wang , Alena M. Sheveleva , Kai Lyu , Xue Han , Floriana Tuna , Eric J. L. Mcinnes , Chiu C. Tang , Lifei Liu , Buxing Han , Emma K. Gibson , C. Richard A. Catlow , Sihai Yang , Martin Schroeder Ccs Chemistry DOI: 10.31635/ccschem.024.202404991 Diamond Proposal Number(s): [33115] Open Access Show Abstract ▼ Abstract: Catalytic cleavage of β-O-4 linkages is an essential but challenging step in the depolymerisation of lignin. Here, we report the templated electrosynthesis of a hydrophobic metal-organic polyhedral catalyst (Cu-MOP-e), which exhibits excellent hydrothermal stability and exceptional activity for this reaction. The oxidative cleavage of 2-phenoxyacetophenone, 1, a lignin model compound, over Cu-MOP-e at 90 oC for 1 h affords full conversion with yields of the monomer products phenol and benzoic acid of 99%. The reusability of Cu-MOP-e has been confirmed by carrying out ten cycles of reaction. The mechanism of catalyst-substrate binding has been investigated by high resolution synchrotron X-ray powder diffraction, in situ X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy and density functional theory calculations. The combination of optimal porosity and active Cu(II) sites provides confined binding of 2-phenoxyacetophenone, thus promoting the cleavage of β-O-4 linkage under relatively mild conditions.	Dec 2024
	Selective hydrogenolysis of the Csp2-O bond in the furan ring using hydride–proton pairs derived from hydrogen spillover Fangfang Peng , Bin Zhang , Runyao Zhao , Shiqiang Liu , Yuxuan Wu , Shaojun Xu , Luke L. Keenan , Huizhen Liu , Qingli Qian , Tianbin Wu , Haijun Yang , Zhimin Liu , Jikun Li , Bingfeng Chen , Xinchen Kang , Buxing Han Chemical Science 6 DOI: 10.1039/D4SC05751A Open Access Show Abstract ▼ Abstract: Selective hydrogenolysis of biomass-derived furanic compounds is a promising approach for synthesizing aliphatic polyols by opening the furan ring. However, there remains a significant need for highly efficient catalysts that selectively target the Csp2–O bond in the furan ring, as well as for a deeper understanding of the fundamental atomistic mechanisms behind these reactions. In this study, we present the use of Pt–Fe bimetallic catalysts supported on layered double hydroxides [PtFex/LDH] for the hydrogenolysis of furanic compounds into aliphatic alcohols, achieving over 90% selectivity toward diols and triols. Our findings reveal that the synergy between Pt nanoparticles, atomically dispersed Pt sites and the support facilitates the formation of hydride-proton pair at the Ptδ+⋯O2− Lewis acid–base unit of PtFex/LDH through hydrogen spillover. The hydride specifically targets the Csp2–O bond in the furan ring, initiating an SN2 reaction and ring cleavage. Moreover, the presence of Fe improves the yield of desired alcohols by inhibiting the adsorption of vinyl groups, thereby suppressing the hydrogenation of the furan ring.	Nov 2024
I20-EDE-Energy Dispersive EXAFS (EDE)	Localized thermal levering events drive spontaneous kinetic oscillations during CO oxidation on Rh/Al2O3 Donato Decarolis , Monik Panchal , Matthew Quesne , Khaled Mohammed , Shaojun Xu , Mark Isaacs , Adam H. Clark , Luke L. Keenan , Takuo Wakisaka , Kohei Kusada , Hiroshi Kitagawa , C. Richard A. Catlow , Emma K. Gibson , Alexandre Goguet , Peter Wells Nature Catalysis 70 DOI: 10.1038/s41929-024-01181-w Diamond Proposal Number(s): [21593] Open Access Show Abstract ▼ Abstract: Unravelling kinetic oscillations, which arise spontaneously during catalysis, has been a challenge for decades but is important not only to understand these complex phenomena but also to achieve increased activity. Here we show, through temporally and spatially resolved operando analysis, that CO oxidation over Rh/Al2O3 involves a series of thermal levering events—CO oxidation, Boudouard reaction and carbon combustion—that drive oscillatory CO2 formation. This catalytic sequence relies on harnessing localized temperature episodes at the nanoparticle level as an efficient means to drive reactions in situations in which the macroscopic conditions are unfavourable for catalysis. This insight provides a new basis for coupling thermal events at the nanoscale for efficient harvesting of energy and enhanced catalyst technologies.	Jul 2024
B18-Core EXAFS I11-High Resolution Powder Diffraction	Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts Lutong Shan , Yujie Ma , Shaojun Xu , Meng Zhou , Meng He , Alena M. Sheveleva , Rongsheng Cai , Daniel Lee , Yongqiang Chen , Boya Tang , Bing Han , Yinlin Chen , Lan An , Tianze Zhou , Martin Wilding , Alexander S. Eggeman , Floriana Tuna , Eric J. L. Mcinnes , Sarah J. Day , Stephen P. Thompson , Sarah J. Haigh , Xinchen Kang , Buxing Han , Martin Schroeder , Sihai Yang Communications Materials 5 DOI: 10.1038/s43246-024-00535-y Diamond Proposal Number(s): [33115, 31729] Open Access Show Abstract ▼ Abstract: The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO3-) to ammonia (NH3). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH3 production of 30.0 and 29.0 mg h−1 cm−2, respectively, with a high Faradaic efficiency (FENH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO3- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO3- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH3.	Jun 2024
I19-Small Molecule Single Crystal Diffraction	Direct observation of enhanced iodine binding within a series of functionalized metal-organic frameworks with exceptional irradiation stability Jiangnan Li , Xinran Zhang , Mengtian Fan , Yinlin Chen , Yujie Ma , Gemma Smith , Inigo Vitórica-Yrezábal , Daniel Lee , Shaojun Xu , Martin Schroeder , Sihai Yang Journal Of The American Chemical Society DOI: 10.1021/jacs.4c02405 Diamond Proposal Number(s): [34413] Open Access Show Abstract ▼ Abstract: Optimization of active sites and stability under irradiation are important targets for sorbent materials that might be used for iodine (I2) storage. Herein, we report the direct observation of I2 binding in a series of Cu(II)-based isostructural metal–organic frameworks, MFM-170, MFM-172, MFM-174, NJU-Bai20, and NJU-Bai21, incorporating various functional groups (–H, −CH3, – NH2, –C≡C–, and −CONH–, respectively). MFM-170 shows a reversible uptake of 3.37 g g–1 and a high packing density of 4.41 g cm–3 for physiosorbed I2. The incorporation of −NH2 and –C≡C– moieties in MFM-174 and NJU-Bai20, respectively, enhances the binding of I2, affording uptakes of up to 3.91 g g–1. In addition, an exceptional I2 packing density of 4.83 g cm–3 is achieved in MFM-174, comparable to that of solid iodine (4.93 g cm–3). In situ crystallographic studies show the formation of a range of supramolecular and chemical interactions [I···N, I···H2N] and [I···C≡C, I–C═C–I] between −NH2, –C≡C– sites, respectively, and adsorbed I2 molecules. These observations have been confirmed via a combination of solid-state nuclear magnetic resonance, X-ray photoelectron, and Raman spectroscopies. Importantly, γ-irradiation confirmed the ultraresistance of MFM-170, MFM-174, and NJU-Bai20 suggesting their potential as efficient sorbents for cleanup of radioactive waste.	May 2024

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