Silica-modified Pt/TiO_(2) catalysts with tunable suppression of strong metal-support interaction for cinnamaldehyde hydrogenation

Tuning Strong Metal-support Interactions(SMSI)is a key strategy to obtain highly active catalysts,but conventional methods usually enable TiO_(x) encapsulation of noble metal components to minimize the exposure of noble metals.This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles(NPs)with the supported TiO_(2),achieving the moderate suppression of SMSI effects.The introduction of silica inhibits this encapsulation,as reflected in the characterization results such as XPS and HRTEM,while the Ti^(4+) to Ti^(3+) conversion due to SMSI can still be found on the support surface.Furthermore,the hydrogenation of cinnamaldehyde(CAL)as a probe reaction revealed that once this encapsulation behavior was suppressed,the adsorption capacity of the catalyst for small molecules like H_(2) and CO was enhanced,which thereby improved the catalytic activity and facilitated the hydrogenation of CAL.Meanwhile,the introduction of SiO_(2) also changed the surface structure of the catalyst,which inhibited the occurrence of the acetal reaction and improved the conversion efficiency of C=O and C=C hydrogenation.Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.

Strong metal–support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Achieving asymmetric redox chemistry for oxygen evolution reaction through strong metal-support interactions

Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redox chemistry through elaborate surface OO–Ru–OH and bulk Ru–O–Ni/Fe coordination moieties within single-atom Ru-decorated defective NiFe LDH nanosheets(Ru@d-NiFe LDH)in conjunction with strong metal-support interactions(SMSI).Rigorous spectroscopic characterization and theoretical calculations indicate that single-atom Ru can delocalize the O 2p electrons on the surface and optimize d-electron configurations of metal atoms in bulk through SMSI.The^(18)O isotope labeling experiment based on operando differential electrochemical mass spectrometry(DEMS),chemical probe experiments,and theoretical calculations confirm the encouraged surface lattice oxygen,stabilized bulk lattice oxygen,and enhanced adsorption of oxygen-containing intermediates for bulk metals in Ru@d-NiFe LDH,leading to asymmetric redox chemistry for OER.The Ru@d-NiFe LDH electrocatalyst exhibits exceptional performance with an overpotential of 230 mV to achieve 10 mA cm^(−2)and maintains high robustness under industrial current density.This approach for achieving asymmetric redox chemistry through SMSI presents a new avenue for developing high-performance electrocatalysts and instills confidence in its industrial applicability.

Unification of Gravitational and Strong Interaction Fields Using Partial Gauge Symmetry

We propose the new field potential by maintaining both the symmetry of the scalar gauge and the conservation law keeping N?ether’s theorem, while disregarding the symmetry of the vector gauge. The new potential forms like the well-type potential where a particle behaves almost freely but is very hard to escape without external energy, which can be interpreted as local confinement and asymptotic freedom. By assuming a 2-dimensional metric tensor in 4-dimensional space-time, we suggest the existence of 3 kinds of particles that resemble QCD with 3 color charges. We also show that the mass term exists but comes to zero and derive the charge and spin values. We can regard the particle with this new potential as a gluon, and the interaction in this well-type potential as a strong interaction for the properties of mass, charge, spin, and its behavior. We suggest the eight-fold way with this new particle, which is similar to the existing method based on SU (3) symmetry. Even though the strong interaction has been analyzed in the standard model and string theory, we build a new consistent model based on the theory of relativity including Riemann geometry, and show the unification of gravitational and strong interactional field.

Coexistence of antiferromagnetism and unconventional superconductivity in a quasi-one-dimensional flat-band system:Creutz lattice

We study the coexistence of antiferromagnetism and unconventional superconductivity on the Creutz lattice which shows strictly flat bands in the noninteracting regime.The famous renormalized mean-field theory is used to deal with strong electron-electron repulsive Hubbard interaction in the effective low-energy t-J model,the superfluid weight of the unconventional superconducting state has been calculated via the linear response theory.An unconventional superconducting state with both spin-singlet and staggered spin-triplet pairs emerges beyond a critical antiferromagnetic coupling interaction,while antiferromagnetism accompanies this state.The superconducting state with only spin-singlet pairs is dominant with paramagnetic phase.The A phase is analogous to the pseudogap phase,which shows that electrons go to form pairs but do not cause a supercurrent.We also show the superfluid behavior of the unconventional superconducting state and its critical temperature.It is proven directly that the flat band can effectively raise the critical temperature of superconductivity.It is implementable to simulate and control strongly-correlated electrons'behavior on the Creutz lattice in the ultracold atoms experiment or other artificial structures.Our results may help the understanding of the interplay between unconventional superconductivity and magnetism.

INTERACTION OF STRONG AND WEAK SINGULARITIES FOR HYPERBOLIC SYSTEM OF CONSERVATION LAWS IN MULTIDIMENSIONAL SPACE

In this paper we study the interaction of strong and weak singularities for hyperbolic system of conservation laws in multidimensional space. Under the assumption of transversal intersect of the shock front with the bicharacteristics bearing weak singularities we proved a theorem on regularity propagation across the shock front.

Boron Nanosheet-Supported Rh Catalysts for Hydrogen Evolution:A New Territory for the Strong Metal-Support Interaction Effect

High-efficiency electrochemical hydrogen evolution reaction(HER)offers a promising strategy to address energy and environmental crisis.Platinum is the most effective electrocatalyst for the HER.However,challenging scarcity,valuableness,and poor electrochemical stability still hinder its wide application.Here,we designed an outstanding HER electrocatalyst,highly dispersed rhodium(Rh)nanoparticles with an average diameter of only 3 nm supported on boron(B)nanosheets.The HER catalytic activity is even comparable to that of commercial platinum catalysts,with an overpotential of only 66 mV in 0.5 M H_(2)SO_(4) and 101 mV in 1 M KOH to reach the current density of 10 mA cm−2.Meanwhile,the catalyst exhibited impressive electrochemical durability during long-term electrochemical processes in acidic and alkaline media,even the simu-lated seawater environment.Theoretical calculations unraveled that the structure-activity relationship between B(104)crystal plane and Rh(111)crystal plane is beneficial to the release of hydrogen,and surface O plays a vital role in the catalysis process.Our work may gain insights into the development of supported metal catalysts with robust catalytic performance through precise engineering of the strong metal-supported interaction effect.

Highly integrated sulfur cathodes with strong sulfur/high-strength binder interactions enabling durable high-loading lithium-sulfur batteries

The development of high-sulfur-loading Li-S batteries is a key prerequisite for their commercial applications.This requires to surmount the huge polarization,severe polysulfide shuttling and drastic volume change caused by electrode thickening.High-strength polar binders are ideal for constructing robust and long-life high-loading sulfur cathodes but show very weak interfacial interaction with non-polar sulfur materials.To address this issue,this work devises a highly integrated sulfur@polydopamine/highstrength binder composite cathodes,targeting long-lasting and high-sulfur-loading Li-S batteries.The super-adhesion polydopamine(PD)can form a uniform nano-coating over the graphene/sulfur(G-S)surface and provide strong affinity to the cross-linked polyacrylamide(c-PAM)binder,thus tightly integrating sulfur with the binder network and greatly boosting the overall mechanical strength/conductivity of the electrode.Moreover,the PD coating and c-PAM binder rich in polar groups can form two effective blockades against the effusion of soluble polysulfides.As such,the 4.5 mg cm−2 sulfur-loaded G-S@PD-c-PAM cathode achieves a capacity of 480 mAh g−1 after 300 cycles at 1 C,while maintaining a capacity of 396 mAh g−1 after 50 cycles at 0.2 C when the sulfur loading rises to 9.1 mg cm−2.This work provides a system-wide concept for constructing high-loading sulfur cathodes through integrated structural design.

Strong metal‐support interaction boosting the catalytic activity of Au/TiO_(2) in chemoselective hydrogenation

Gold catalysts have been reported as highly effective catalysts in various oxidation reactions.However,for chemoselective hydrogenation reactions,gold‐based catalysts normally show much lowercatalytic activity than platinum group metals,even though their selectivities are excellent.Here,wereport that the chemoselective hydrogenation activity of 3‐nitrostyrene to 3‐vinylaniline overAu/TiO_(2)can be enhanced up to 3.3 times through the hydrogen reduction strategy.It is revealedthat strong metal‐support interaction,between gold nanoparticles(NPs)and TiO_(2)support,is introducedthrough hydrogen reduction,resulting in partial dispersion of reduced TiOx on the Au surface.The partially covered Au not only increases the perimeter of the interface between the gold NPs andthe support,but also benefits H_(2)activation.Reaction kinetic analysis and H_(2)‐D2 exchange reactionshow that H_(2)activation is the critical step in the hydrogenation of 3‐nitrostyrene to 3‐vinylaniline.Density functional theory calculations verify that hydrogen dissociation and hydrogen transfer arefavored at the interface of gold NPs and TiO_(2)over the hydrogen‐reduced Au/TiO_(2).This study providesinsights for fabricating highly active gold‐based catalysts for chemoselective hydrogenationreactions.

STRONGLY OBLIQUE INTERACTIONS BETWEEN INTERNAL SOLITARY WAVES WITH THE SAME MODE

In this paper, by using the Lagrangian coordinates, the strongly oblique interactions between solitary waves with the same mode in a stratified fluid ape discussed, which includes the shallow fluid case and deep fluid case. It is found that the interactions are described by the KP equation for the shallow fluid case, the two-dimensional intermediate long wave equation (2D-ILW equation) for the deep fluid case and the two-dimensional BO equation (2D-BO equation) for the infinite deep fluid case.

Electromagnetically Induced Transparency in a Cold Gas with Strong Atomic Interactions

Electromagnetically induced transparency （EIT） is investigated in a system of cold, interacting cesium Rydberg atoms. The utilized cesium levels 6S1/2, 6P3/2 and nD5/2 constitute a cascade three-level system, in which a coupling laser drives the Rydberg transition, and a probe laser detects the EIT signal on the 6S1/2 to 6/23/2 transition. Rydberg EIT spectra are found to depend on the strong interaction between the Rydberg atoms. Diminished EIT transparency is obtained when the Rabi frequency of the probe laser is increased, whereas the corresponding linewidth remains unchanged. To model the system with a three-level Linclblad equation, we introduce a Rydberg-level dephasing rate γ3 = κ×（P33/Ωp）^2, with a value κ that depends on the ground-state atom density and the Rydberg level, The simulation results are largely consistent with the measurements. The experiments, in which the principal quantum number is varied between 30 and 43, demonstrate that the EIT reduction observed at large Ωp is due to the strong interactions between the Rydberg atoms.

Dry Reforming of Ethane over FeNi/Al-Ce-O Catalysts:Composition-Induced Strong Metal-Support Interactions

Dry reforming of ethane(DRE)has received significant attention because of its potential to produce chemical raw materials and reduce carbon emissions.Herein,a composition-induced strong metal-support interaction(SMSI)effect over FeNi/Al-Ce-O catalysts is revealed via X-ray photoelectron spectroscopy(XPS),H_(2)-temperature programmed reduction(TPR),and energy dispersive X-ray spectroscopy(EDS)elemental mapping.The introduction of Al into Al-Ce-O supports significantly influences the dispersion of surface active components and improves the catalytic performance for DRE over supported FeNi catalysts due to enhancement of the SMSI effect.The catalytic properties,for example,C_(2)H_(6) and CO_(2) conversion,CO selectivity and yield,and turnover frequencies(TOFs),of supported FeNi catalysts first increase and then decrease with increasing Al content,following the same trend as the theoretical effective surface area(TESA)of the corresponding catalysts.The FeNi/Ce-Al_(0.5) catalyst,with 50%Al content,exhibits the best DRE performance under steady-state conditions at 873 K.As observed by with in situ Fourier transform infrared spectroscopy(FTIR)analysis,the introduction of Al not only increases the content of surface Ce3+and oxygen vacancies but also promotes the dispersion of surface active components,which further alters the catalytic properties for DRE over supported FeNi catalysts.

Strong Interaction Effect on Jet Energy Loss with Detailed Balance

The strong force effect on gluon distribution of quark-gluon plasma and its influence on jet energy loss with detailed balance are studied. We solve the possibility equation and obtain the value of non-extensive parameter q. In the presence of strong interaction, more gluons stay at low-energy state than the free gluon case. The strong interaction effect is found to be important for jet energy loss with detailed balance at intermediate jet energy. The energy gain via absorption increases with the strong interaction. This will affect the nuclear modification factor RAA and the parameter of q at intermediate jet energy.

Exploration of Strong Metal-Support Interaction in Heterogeneous Catalysts by in situ Transmission Electron Microscopy

The phenomenon of strong metal-support interaction(SMSI)observed in supported metal catalysts,usually accompanied by the formation of the encapsulation layer on metal nanoparticles,has attracted extensive research attention due to its significance in heterogeneous catalysis.Notably,great progress has been made in recent years in investigating SMSI by in situ transmission electron microscopy(TEM),along with an enhanced comprehension of the underlying mechanisms governing SMSI formation.This emerging topic summarizes recent progress utilizing in situ TEM to study the interaction between metal and support and the relationship between the structure and performance of the supported catalyst under reaction conditions.A brief perspective about the use of in situ TEM for further study of SMSI is also presented,showing prospects in this field that will stimulate further upsurging research in promoting the catalytic efficiency of supported catalysts.

Investigating the impact of dynamic structural changes of Au/rutile catalysts on the catalytic activity of CO oxidation

The surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts.When metals are supported on reducible oxides,dynamic surface reconstruction phenomena,including strong metal–support interaction(SMSI)and oxygen vacancy formation,complicate the determination of the structural–functional relationship at the active sites.Here,we performed a systematic investigation of the dynamic behavior of Au nanocatalysts supported on flame‐synthesized TiO_(2),which takes predominantly a rutile phase,using CO oxidation above room temperature as a probe reaction.Our analysis conclusively elucidated a negative correlation between the catalytic activity of Au/TiO_(2) and the oxygen vacancy at the Au/TiO_(2) interface.Although the reversible formation and retracting of SMSI overlayers have been ubiquitously observed on Au/TiO_(2) samples,the catalytic consequence of SMSI remains inconclusive.Density functional theory suggests that the electron transfer from TiO_(2) to Au is correlated to the presence of the interfacial oxygen vacancies,retarding the catalytic activation of CO oxidation.

Strong coupled spinel oxide with N-rGO for high-efficiency ORR/OER bifunctional electrocatalyst of Zn-air batteries

The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to replace noble metal electrocatalysts.Hence,in this study,we investigate a novel and low-cost bifunctional electrocatalyst consisting of ZnCoMnO_(4) anchored on nitrogen-doped graphene oxide(ZnCoMnO_(4)/N-rGO).Benefiting from the strong Co-N interaction in ZnCoMnO_(4) and the coupled conductive N-rGO,the catalysts exhibit high electrocatalytic activity.Moreover,density functional theory calculations support the dominant role of the strong Co-N electronic interaction,which leads to ZnCoMnO_(4)/N-rGO having more favorable binding energies with O2 and H_(2) O,resulting in fast reaction kinetics.The obtained ZnCoMnO_(4)/N-rGO electrocatalyst exhibits superb bifunctional activity,with a half-wave potential of 0.83 V for the oxygen reduction reaction and a low onset potential of 1.57 V for the oxygen evolution reaction in 0.1 M KOH solution.Furthermore,a Zn-air battery driven by the ZnCoMnO_(4)/N-rGO catalyst shows remarkable discharge/charge performance,with a power density of 138.52 mW cm^(-2) and longterm cycling stability for 48 h.This work provides a promising multifunctional electrocatalyst based on non-noble metals for the storage and conversion of renewable energy.

Three Clifford Algebras for Four Kinds of Interactions

Three Clifford algebras are sufficient to describe all interactions of modern physics: The Clifford algebra of the usual space is enough to describe all aspects of electromagnetism, including the quantum wave of the electron. The Clifford algebra of space-time is enough for electro-weak interactions. To get the gauge group of the standard model, with electro-weak and strong interactions, a third algebra is sufficient, with only two more dimensions of space. The Clifford algebra of space allows us to include also gravitation. We discuss the advantages of our approach.

Strong hetero-interface interaction in 2D/2D WSe_(2)/ZnIn_(2)S_(4) heterostructures for highly-efficient photocatalytic hydrogen generation

Green hydrogen is urgently required for sustainable development of human beings and rational construction of heterostructures holds great promising for photocatalytic hydrogen generation.Herein,2D/2D WSe_(2)/ZnIn_(2)S_(4) heterostructures with strong hetero-interface interaction and abundant contact were constructed via an impregnation-annealing strategy.Efficient charge transfer from ZnIn_(2)S_(4) to WSe_(2)was evidenced by transient absorption spectroscopy in crafted heterostructures owing to the tight and2D face-to-face contact.As a result,the prepared WSe_(2)/ZnIn_(2)S_(4) heterostructures exhibited boosted photocatalytic performance and a highest hydrogen evolution rate of 3.377 mmol/(g h)was achieved with an apparent quantum yield of 45.7%at 420 nm.The work not only provides new strategies to achieve efficient 2D/2D heterostructures but also paves the way for the development of green hydrogen in the future.

A Review on Metal-support Interaction in Automotive Catalysts

TWC-equipped exhausts are widely used in gasoline-fueled vehicles to meet stringent emission regulations. The main components in TWCs are precious metals such as palladium (Pd), platinum (Pt), and rhodium (Rh) as the active component, and inorganic oxides such as γ-alumina (Al 2 O 3 ), ceria (CeO 2 ), zirconia (ZrO 2 ) and ceria-zirconia (CeO 2-ZrO 2 ) are used as the support. Interaction of precious metals and support plays an important role in the thermal stability and catalytic performance of TWCs. The support can improve the dispersion of precious metals and suppress the sintering of precious metals at high temperature. In the same, precious metals can also enhance the redox performance and oxygen storage capacity of support. This paper reviews the reaction phenomenon and mechanism of precious metals (Pt, Pd, Rh) and supports such as Al 2 O 3 , CeO 2-based composite oxides.

Towards the Unification of All Interactions (The First Part: The Spinor Wave)

For the unification of gravitation with electromagnetism, weak and strong interactions, we use a unique and very simple framework, the Clifford algebra of space . We enlarge our previous wave equation to the general case, including all leptons, quarks and antiparticles of the first generation. The wave equation is a generalization of the Dirac equation with a compulsory non-linear mass term. This equation is form invariant under the group of the invertible elements in the space algebra. The form invariance is fully compatible with the gauge invariance of the standard model. The wave equations of the different particles come by Lagrange equations from a Lagrangian density and this Lagrangian density is the sum of the real parts of the wave equations. Both form invariance and gauge invariance are exact symmetries, not only partial or broken symmetries. Inertia is already present in the part of the gauge group and the inertial chiral potential vector simplifies weak interactions. Relativistic quantum physics is then a naturally yet unified theory, including all interactions.