Structural phase transformation of quantum spin liquid herbertsmithite via pressure induced enhancement of the cooperative Jahn-Teller effect and antisite disorder.

Herbertsmithite, Cu3Zn(OH)6Cl2, serves as one of the most promising candidates for quantum spin liquids with a perfect quantum kagome Heisenberg antiferromagnetic system. It can comprise an ideal model system for studying the compression response of the unique structure as well as exotic properties of kagome quantum spin liquid materials, which is of fundamental importance from both scientific and technological viewpoints. In this work, the structural evolution of herbertsmithite was investigated via in situ X-ray diffraction and Raman scattering techniques up to 30 GPa. The trigonal herbertsmithite structure transformed into a monoclinic clinoatacamite-like structure at 12.6 GPa. High pressure seems to act in a reverse way as Zn-doping for herbertsmithite, with the distortion degree of the system changing continuously. The occurrence of the displacive and reversible phase transition between the polymorphs is a consequence of the interplay between the external pressure and cooperative Jahn-Teller (JT) effect, aided by the presence of antisite mutual substitution of magnetic Cu2+ ions and nonmagnetic Zn2+ ions between the kagome layer and interlayer sites.

Interplay between External High Pressure and Intrinsic Jahn-Teller Effect in the Compression Behavior of Clinoatacamite.

Clinoatacamite (γ-Cu2(OH)3Cl) possesses a geometrically frustrated kagome lattice for the S = 1/2 antiferromagnetic spin system. Thus, it is deemed as the mother compound of many promising quantum spin liquid materials. Here, we synthesized clinoatacamite consisting of homogeneous octahedron-like particles with an average size of 1-2 µm via a hydrothermal strategy. Clinoatacamite crystallizes in a monoclinic lattice composed of Jahn-Teller distorted Cu(OH)6 and Cu(OH)4Cl2 octahedrons. The bonding nature of clinoatacamite is characterized using Raman scattering and FTIR absorption spectroscopies, which reveal the existence of trimeric hydrogen bonds. The magnetic measurements indicate that at temperatures below about 6 K, the magnetic response of the prepared samples is dominated by weak ferromagnetic contributions. The compression behavior is investigated by in situ high-pressure synchrotron radiation X-ray diffraction and Raman scattering spectroscopy. An isostructural phase transition is observed at about 8.4 GPa, which is evidenced by the anomalies in the variation curves of the lattice parameters and Raman scattering frequencies with pressure. The occurrence of the isostructural phase transition is attributed to the competition and cooperation of the external pressure and intrinsic Jahn-Teller effect, together with the interplay of intrastructural hydrogen bonding.

Interface-Induced Self-Assembly Strategy Toward 2D Ordered Mesoporous Carbon/MXene Heterostructures for High-Performance Supercapacitors.

Two-dimensional transition metal carbonitrides (MXene) have demonstrated great potential in many fields. However, the serious aggregation and poor thermodynamic stability of MXene greatly hinder their applications. Here, an interface-induced self-assembly strategy to synthesize ordered mesoporous carbon/Ti3 C2 Tx heterostructures (OMCTs) was developed. In this method, the composite monomicelles formed by Pluronic F127 and low-molecular-weight phenolic resol self-assembled on the surface of Ti3 C2 Tx to prevent the restacking of Ti3 C2 Tx and maintain its thermostability. The obtained OMCTs possessed high specific surface areas (259-544 m2 g-1 ), large pore volumes (0.296-0.481 cm3 g-1 ), and excellent thermodynamic stability (up to 600 °C). Benefiting from these advantages, OMCTs serving as the electrode materials for supercapacitor exhibited superior supercapacitor performances, including high capacitance of 247 F g-1 at 0.2 A g-1 , satisfactory rate performance of 190 F g-1 at 5 A g-1 , and cyclability.

Interface-Induced Self-Assembly Strategy Toward 2D Ordered Mesoporous Carbon/MXene Heterostructures for High-Performance Supercapacitors.

Invited for this month's cover is the group of Zhen-An Qiao at the Jilin University. The image shows the application of 2D ordered mesoporous carbon/MXene heterostructures in supercapacitors. The Full Paper itself is available at 10.1002/cssc.202101374.