Science - USA (2021-12-24)

the less acidic P-containing unwashed sam-
ple (fig. S21) ( 16 ). These preliminary labo-
ratory results show that ZEO-1 can compete
with the highly optimized USY and also the
recently reported PST-32 and PST-2 ( 9 ) and
thus has a high potential as a component of
cracking catalysts.

REFERENCES AND NOTES

1. Reza Sadeghbeigi,Fluid Catalytic Cracking Handbook(Gulf
   Publishing, ed. 2, 2000).


2. Ch. Baerlocher, L. B. McCusker, Database of Zeolite Structures
   (2017); http://www.iza-structure.org/databases.


3. L. Burel, N. Kasian, A. Tuel,Angew. Chem. Int. Ed. 53 ,
   1360 – 1363 (2014).


4. H. Xuet al.,Angew.Chem.Int.Ed. 53 , 1355– 1359
   (2014).


5. Y. Chenet al.,Chemistry 25 , 3219–3223 (2019).


6. Y. Wanget al.,Inorg. Chem. Front. 4 , 1654–1659 (2017).


7. R. Fricke, H.-L. Zubowa, M. Richter, H. Kosslick,C. R. Chim. 8 ,
   549 – 559 (2005).


8. The structure commission of the International Zeolite
   Association (SC-IZA) assigns three-letter Zeolite Framework
   Type codes to approved zeolite structures. Interrupted
   framework codes are preceded by a hyphen ( 2 ).


9. H. Leeet al.,Science 373 , 104–107 (2021).


10. G. M. Sheldrick,Acta Crystallogr. A Found. Adv. 71 ,3– 8
    (2015).


11. P. Guoet al.,Nature 524 , 74–78 (2015).


12. C. Baerlocher, T. Weber, L. B. McCusker, L. Palatinus,
    S. I. Zones,Science 333 , 1134–1137 (2011).


13. J. Shinet al.,Angew. Chem. Int. Ed. 55 , 4928– 4932
    (2016).


14. X. Li, C. Li, J. Zhang, C. Yang, H. Shan,J. Nat. Gas Chem. 16 ,
    92 – 99 (2007).


15. H. E. van der Bij, B. M. Weckhuysen,Chem. Soc. Rev. 44 ,
    7406 – 7428 (2015).


16. W. Vermeiren, J.-P. Gilson,Top. Catal. 52 , 1131– 1161
    (2009).


17. I. Pellejeroet al.,Ind. Eng. Chem. Res. 46 , 2335–2341 (2007).

ACKNOWLEDGMENTS
We are indebted to M. J. de la Mata (SIdI-UAM) for her expedited
help in collecting the solid-state nuclear magnetic resonance
spectra and to the ALBA staff for collaboration in collecting the
SPXRD data at the Spanish ALBA synchrotron beamline BL04
(MSPD).Funding:We acknowledge financial support from the
National Natural Science Foundation of China (grants 21601004,
21776312, and 22078364); the Natural Science Foundation
of the Higher Education Institutions of Anhui Province, China
(grant KJ2020A0585); and MCIN/AEI/10.13039/501100011033,
Spain (project PID2019-105479RB-I00). The cRED data was
collected at the Electron Microscopy Center (EMC), Department
of Materials and Environmental Chemistry (MMK) in Stockholm
University, with the support of the Swedish Research Council
(grant 1444205) and the Knut and Alice Wallenberg Foundation
(KAW) (grant 2012-0112) through the 3DEM-NATUR project.
Use of the Advanced Photon Source at Argonne National
Laboratory was supported by the US Department of Energy,
Office of Science, Office of Basic Energy Sciences, under contract
DE-AC02-06CH11357. W.F. gratefully acknowledges support from
the US Department of Energy, Office of Science, Basic Energy
Sciences, Materials Sciences and Engineering Division, under
award DE-SC0019170.Author contributions:F.-J.C. designed
the project. J.L., X.C., M.A.C., and F.-J.C. supervised the work.
Q.-F.L., S.Z., and F.-J.C. carried out the synthesis work. J.L. solved
the structure. Z.R.G. and C.L. analyzed the topology. J.C., Z.L.,
and X.C. carried out the FCC reaction. X.L., W.F., C.L., Z.R.G., and
M.A.C. performed the physicochemical characterization. Z.R.G.
and M.A.C. performed the large molecule analysis. Z.R.G., C.L., J.L.,
and M.A.C. prepared the draft. All the authors discussed the results
and revised the manuscript.Competing interests:Q.-F.L., Z.R.G.,
C.L., J.L., and F.-J.C. have filed a patent on zeolite ZEO-1 (China patent
application no. 202011346698.4). Z.R.G. and J.L. are affiliated with
the company holding the rights on that patent.Data and materials
availability:All data are available in the main text or the supplementary
materials. Crystallographic parameters for the structure of as-made
and calcined ZEO-1 refined against SPXRD and calcined ZEO-1 refined

against cRED data are archived at the Cambridge Crystallographic

Data Center (CCDC) (www.ccdc.cam.ac.uk) under reference

nos. CCDC 2112774 to 2112776.

SUPPLEMENTARY MATERIALS

science.org/doi/10.1126/science.abk3258

Materials and Methods

Figs. S1 to S22

Tables S1 to S14

References ( 18 – 28 )

Movie S1

Data Files S1 to S3

6 July 2021; resubmitted 21 July 2021

Accepted 28 October 2021

10.1126/science.abk3258

ULTRAFAST MAGNETISM

Terahertz lightÐdriven coupling of antiferromagnetic

spins to lattice

Evgeny A. Mashkovich1,2*, Kirill A. Grishunin^1 , Roman M. Dubrovin^3 , Anatoly K. Zvezdin4,5,

Roman V. Pisarev^3 , Alexey V. Kimel^1

Understanding spin-lattice coupling represents a key challenge in modern condensed matter

physics, with crucial importance and implications for ultrafast and two-dimensional magnetism.

The efficiency of angular momentum and energy transfer between spins and the lattice imposes

fundamental speed limits on the ability to control spins in spintronics, magnonics, and magnetic data

storage. We report on an efficient nonlinear mechanism of spin-lattice coupling driven by terahertz

light pulses. A nearly single-cycle terahertz pulse resonantly interacts with a coherent magnonic

state in the antiferromagnet cobalt difluoride (CoF 2 ) and excites the Raman-active terahertz phonon.

The results reveal the distinctive functionality of antiferromagnets that allows ultrafast spin-lattice

coupling using light.

U

nderstanding how to control the spin-

lattice interaction is a cornerstone for

several hot topics of contemporary mag-

netic research, including ultrafast mag-

netism ( 1 ) and phononic control of

magnetism ( 2 – 6 ), two-dimensional (2D) mag-

netism ( 7 ), magnonics ( 8 – 10 ), and spintronics

( 11 ). Although this interaction is well under-

stood in the vicinity of thermodynamic equi-

librium, large-amplitude oscillations of atoms

result in an essentially anharmonic lattice dy-

namics with an increasingly important role of

higher-order terms in the atomic free energy

( 12 ). For instance, driving coherent lattice vib-

rations into an anharmonic regime can promote

energy transfer between different, otherwise

noninteracting phononic modes via fully co-

herent phonon-phonon interactions ( 12 ). Sim-

ilarly, one can expect a nonlinear mechanism

of light-driven phonon-magnon coupling

( 13 – 15 ) and even anticipate nontrivial ultrafast

phenomena associated with the physics of the

Einstein–de Haas effect ( 16 ). Although several

nonlinear mechanisms of phononic control of

magnetism have been demonstrated theoret-

ically ( 3 ) and experimentally ( 4 – 6 , 17 ), along-

side intense research interest devoted to

exploring terahertz (THz) magnonics, under-

standing the nonlinear mechanism of energy

transfer from THz magnons to THz phonons

remains outstanding.

Antiferromagnets represent an appealing

playground for the search for new channels

of spin-lattice coupling in the THz regime.

Their spin structure can be modeled in the

simplest case by two antiparallel sublattices

with the net magnetizationsM 1 andM 2 ,|M 1 |=

|M 2 |. Alternatively, for describing the magnetic

order, it is convenient to introduce the net

magnetization vectorM=M 1 +M 2 and the

Néel (antiferromagnetic) vectorL=M 1 −M 2.

Typically, the frequencies of spin resonances

in antiferromagnets are close to those of THz

optical phonons. The objective of this study is

therefore to use intense, nearly single-cycle

THz pulses ( 18 ) to drive coherent spin oscil-

lations ( 9 ) and promote interactions between

otherwise noninteracting magnonic and pho-

nonic modes.

To demonstrate light-driven spin-lattice coup-

ling, we selected a cobalt difluoride (CoF 2 )

single-crystal plate with the tetragonal rutile

crystal structure. Below the Néel temperature

TN= 39 K, CoF 2 is a collinear antiferromagnet

with a strong piezomagnetic effect ( 19 ). In a

unit cell, the spins of Co2+ions at the cell’s

center are antiparallel to those at the cell’s

corners ( 20 ). These two types of ions form the

two antiferromagnetic sublattices with the net

1608 24 DECEMBER 2021•VOL 374 ISSUE 6575 science.orgSCIENCE

(^1) Institute for Molecules and Materials, Radboud University,
6525 AJ Nijmegen, Netherlands.^2 Institute of Physics II,
University of Cologne, D-50937 Cologne, Germany.^3 Ioffe
Institute, Russian Academy of Sciences, St. Petersburg
194021, Russia.^4 Prokhorov General Physics Institute,
Russian Academy of Sciences, Moscow 119991, Russia.
(^5) Moscow Institute of Physics and Technology, Dolgoprudnyi
141700, Russia.
*Corresponding author. Email: [email protected]
RESEARCH | REPORTS