Confined cobalt single-atom catalysts with strong electronic metal-support interactions based on a biomimetic self-assembly strategy

Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η10 at 288 mV;Tafel slope of 44 mV dec-1),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

Correction of distorted X-ray absorption spectra collected with capillary sample cell

In certain exceptional cases,capillary samples must be used to measure X-ray absorption spectra(XAS).However,the inho-mogeneous thickness of capillary samples causes XAS distortion.This study discusses the distortion and correction of the XAS curve caused by the inhomogeneous thickness of capillary samples.The relationship between the distorted XAS curveμ′d_(eq)(measured values)and the real absorption coefficientμ_(s)d_(eq)(true values)of the sample was established.The distortion was slight and negligible when the vertical size(2h)of the X-ray beam spot was smaller than 60%of the capillary tube’s inner diameter(2R_(in)).When h/R_(in)>1,X-ray leakage is inevitable and should be avoided during measurement.Partial X-ray leakage caused by an X-ray beam spot size larger than the inner diameter of the capillary tube leads to serious compressed distortion of the XAS curve.When h/R_(in)<1,the distorted XAS data were well corrected.Possible errors and their influence on the corrected XAS are also discussed.Simulations and corrections for distortions verify the feasibility and effectiveness of the corrected method.

Silicon PIN photodiode applied to acquire high-frequency sampling XAFS spectra

Experimental techniques based on SR facilities have emerged with the development of synchrotron radiation(SR)sources.Accordingly,detector miniaturization has become significant for the development of SR experimental techniques.In this study,the miniaturization of a detector was achieved by coupling a commercial silicon PIN photodiode(SPPD)into a beamstop,aiming for it not only to acquire X-ray absorption fine structure(XAFS)spectra,but also to protect the subsequent two-dimensional detector from high-brilliance X-ray radiation damage in certain combination techniques.This mini SPPD detector coupled to a beamstop was used as the rear detector in both the conventional sampling scheme and novel high-frequency(HF)sampling scheme to collect the transmission XAFS spectra.Traditional ion chambers were also used to collect the transmission XAFS spectra,which were used as the reference.These XAFS spectra were quantitatively analyzed and compared;the results demonstrated that the XAFS spectra collected by this SPPD in both the conventional sampling scheme and HF sampling scheme are feasible.This study provides a new detector-selection scheme for the acquisition of the quick-scanning XAFS(QXAFS)and HF sampling XAFS spectra.The SPPD detector presented in this study can partially meet the requirements of detector miniaturization.

Mesoporous Cu_(3−x)Zn_(x)(BTC)_(2)nanocubes synthesized in deep eutectic solvent and their catalytic performances

To develop high-performance metal-organic frameworks(MOFs)for catalysis is of great importance.Here,we synthesized the mesoporous Cu_(3−x)Zn_(x)(BTC)_(2)(BTC=benzene-1,3,5-tricarboxylate)nanocubes in a deep eutectic solvent of ZnCl_(2)/ethylene glycol solution.The route can proceed at room temperature and the reaction time needed is shortened to be 30 min,which is superior to the conventional solvothermal route that usually needs high temperature and long reaction time.The formation mechanism of the mesoporous Cu_(3−x)Zn_(x)(BTC)_(2)nanocubes in deep eutectic solvent(DES)was investigated by in situ synchrotron X-ray diffraction/small angle X-ray scattering/X-ray absorption fine structure conjunction technique.The mesoporous Cu_(3−x)Zn_(x)(BTC)_(2)nanocubes exhibit high catalytic activity and reusability for cyanosilylation reaction of benzaldehyde and aerobic oxidation reaction of benzylic alcohol.

A novel SAXS/XRD/XAFS combined technique for in-situ timeresolved simultaneous measurements

Synchrotron radiation based combined technique can provide multiple structural information simultaneously,which is an important development direction of structural detection.In this study,a novel small-angle X-ray scattering/X-ray diffraction/X-ray absorption fine structure(SAXS/XRD/XAFS)combined setup was constructed,where an area detector,a curved detector,and a point detector are,respectively,used for the measurements of SAXS,XRD,and XAFS signals.A detailed description about the combined setup was given.A minitype diamond detector coupled to a SAXS beamstop was used to record the transmitted X-ray intensity,making the scattering(SAXS and XRD)signal measurement compatible with the absorption(XAFS)signal measurement,avoiding mechanical switching.The two-way sampling strategy was used to acquire XAFS signals,shortening the non-counting time.The two-way and one-way sampling strategies were discussed.High-frequency sampling scheme was used to collect experimental signals,improving the measurement efficiency and signal-to-noise ratio.A detailed description and discussion about the high-frequency scheme were also given in this paper.Except the rotation of monochromator,there is no mechanical movement in measurements,time resolution may reach the level of seconds.Using this SAXS/XRD/XAFS combined setup,SAXS,XRD,and XAFS signals can be acquired simultaneously.With some in-situ sample environment system,the newlydeveloped combined technique can be used to track the structure evolution in complex fluids.During the formation processes of(BiO)2CO3 and ZnAPO-34 particles,the changes of in-situ experimental data with reaction time demonstrate that SAXS/XRD/XAFS combined technique is feasible to track the dynamic process.

A New Route for the Rapid Synthesis of Metal–Organic Frameworks at Room Temperature

Rapid synthesis of metal–organic frameworks(MOFs),especially high-valence MOFs at roomtemperature without external energy,is a challenging topic.In this work,a stable radical solution has been discovered.Various MOFs with versatile metal nodes and ligands were rapidly synthesized at room temperature in the absence of external energy.Especially,MOFs with conjugated ligands achieved instantaneous architecture(in less than 1 s)and quantitative yield.Radicals in the solution play a crucial role in the accelerated kinetics,and the new radical route paves a cyclic pathway for the MOF synthesis.The mechanism has been thoroughly investigated by electron paramagnetic resonance,in situ proton nuclear magnetic resonance,X-ray absorption spectra,in situ small-angle X-ray scattering-wide-angle X-ray scattering,and density functional theory calculations.

Small-angle X-ray scattering study on the orientation of suspended sodium titanate nanofiber induced by applied electric field

Introduction Nanofiber orientation in suspensions determines the performance of nanoparticle suspensions which have potential applications in intelligent control.Material and method Na2Ti3O7 nanofibers were prepared with a hydrothermal method.The orientation degree of Na2Ti3O7 nanofibers in silicone oil has been studied by in situ small-angle X-ray scattering technique.Thünemann–Ruland method was used to extract the distribution widths of Na2Ti3O7 nanofibers in the suspensions.Conclution An empirical formula has been proposed to describe the dependence of nanofiber orientation degree on the external electric-field strength(E)and the nanofiber concentration(C).The results demonstrate that the response of nanofiber orientation to the electric field can be divided into exponential and linear stages before and after the inflection point of electric-field strength(Ec0.09 kV/mm).Low concentration of suspension is more sensitive to the external electric field.The increase in nanofiber concentration will decrease the response sensitivity of nanofiber orientation degree to the change of E.The critical concentration of Na2Ti3O7 nanofibers in the suspension is about 5 wt%.This study is expected to give new clue for the structurally responsive mechanism of anisotropic nanoparticles in suspensions to electric-field strength and particle concentration.