The realization of Kitaev spin liquid, where spins on a honeycomb lattice are coupled ferromagnetically by bond-dependent anisotropic interactions, has been a sought-after dream. 5d iridium oxides α-Li 2 IrO 3 and α-Na 2 IrO 3 with a honeycomb lattice of J eff = 1/2 moments recently emerged as a possible materialization. Strong signature of Kitaev physics, however, was not captured. Here we report the discovery of a complex iridium oxide β-Li 2 IrO 3 with J eff = 1/2 moments on "hyper-honeycomb" lattice, a three-dimensional analogue of honeycomb lattice. A positive Curie-Weiss temperature θ CW ~ 40 K indicated dominant ferromagnetic interactions among J eff = 1/2 moments in β-Li 2 IrO 3 . A magnetic ordering with a small entropy change was observed at T c = 38 K, which, with the application of magnetic field of only 3 T, changed to a fully polarized state of J eff = 1/2 moments. Those results imply that hyper-honeycomb β-Li 2 IrO 3 is located in the vicinity to a Kitaev spin liquid.
In the series of 3d (t 2g ) 1 perovskites, SrVO 3 -CaVO 3 -LaTiO 3 -YTiO 3 ,
Solar hydrogen (H 2 ) evolution from water utilizing covalent organic frameworks (COFs) as heterogeneous photosensitizers has gathered significant momentum by virtue of the COFs’ predictive structural design, long-range ordering, tunable porosity, and excellent light-harvesting ability. However, most photocatalytic systems involve rare and expensive platinum as the co-catalyst for water reduction, which appears to be the bottleneck in the development of economical and environmentally benign solar H 2 production systems. Herein, we report a simple, efficient, and low-cost all-in-one photocatalytic H 2 evolution system composed of a thiazolo[5,4- d ]thiazole-linked COF ( TpDTz ) as the photoabsorber and an earth-abundant, noble-metal-free nickel-thiolate hexameric cluster co-catalyst assembled in situ in water, together with triethanolamine (TEoA) as the sacrificial electron donor. The high crystallinity, porosity, photochemical stability, and light absorption ability of the TpDTz COF enables excellent long-term H 2 production over 70 h with a maximum rate of 941 μmol h –1 g –1 , turnover number TON Ni > 103, and total projected TON Ni > 443 until complete catalyst depletion. The high H 2 evolution rate and TON, coupled with long-term photocatalytic operation of this hybrid system in water, surpass those of many previously known organic dyes, carbon nitride, and COF-sensitized photocatalytic H 2 O reduction systems. Furthermore, we gather unique insights into the reaction mechanism, enabled by a specifically designed continuous-flow system for non-invasive, direct H 2 production rate monitoring, providing higher accuracy in quantification compared to the existing batch measurement methods. Overall, the results presented here open the door toward the rational design of robust and efficient earth-abundant COF–molecular co-catalyst hybrid systems for sustainable solar H 2 production in water.
The first lithium fluorooxoborate LiB 6 O 9 F was synthesized from LiF and B 2 O 3 in an all-solid state reaction at 673 K. Single crystals have been grown by subsequent long-term annealing at 473 K. According to X-ray analysis of the crystal structure [Pna2 1 , Z ϭ 4, a ϭ 7.6555 (1) Å , b ϭ 8.5318(1) Å , c ϭ 10.7894(2) Å , R 1 ϭ 0.0184, wR(all) ϭ 0.0487, 853 independent reflections], the fluorooxoborate anion forms a two-dimensional infinite network with boroxine rings, connected by bridging oxygen atoms constitut-* Prof. Dr. M. Jansen Fax: ϩ49-711-689-1502 E-Mail: M.Jansen@fkf.mpg.de [a]
Spin 1 2 honeycomb materials have gained substantial interest due to their exotic magnetism and possible application in quantum computing. However, in all current materials out-of-plane interactions are interfering with the in-plane order, hence a true 2D magnetic honeycomb system is still of demand. Here, we report the exfoliation of the magnetic semiconductor α-RuCl 3 into the first halide monolayers and the magnetic characterization of the spin 1 2 honeycomb arrangement of turbostratically stacked RuCl 3 monolayers. The exfoliation is based on a reductive lithiation/hydration approach, which gives rise to a loss of cooperative magnetism due to the disruption of the spin 1 2 state by electron injection into the layers. After an oxidative treatment, cooperative magnetism similar to the bulk is restored. The oxidized pellets of restacked single layers feature a magnetic transition at T N = 7 K in the in-plane direction, while the magnetic properties in the out-of-plane direction vastly differ from bulk α-RuCl 3 . The macro- Binary halide nanosheets have been predicted based on chemical intuition 3,4 or ab initio calculations. 7 Yet, no single layer halides have been synthesized so far, even though this class of compounds features an array of interesting electrical and magnetic properties.The magnetic semiconductor α-RuCl 3 is one such example. While it was investigated in the past as a host for intercalants 8,9 and as a lithium ion conductor, 10 current research focuses on its magnetic properties. Due to its layered honeycomb structure of spin 1 2 Ru 3+ centers in combination with spin orbit coupling (SOC), it is one of the few known materials featuring a zigzag antiferromagnetic (AF) ground state below a temperature of T N1 = 8 K. [11][12][13] In the zigzag order, the magnetic moments form ferromagnetic (FM) zigzag chains, whose magnetization direction is opposed to the neighboring chains within the plane. Additionally, there is a further magnetic phase transition observed at T N2 = 14 K. The origin of this transition is currently still under debate. This type of ordering was first observed in Na 2 IrO 3 14-16 and explained by the Kitaev-Heisenberg model, 17,18 which describes that a frustrated spin 1 2 honeycomb arrangement could lead to a variety of interesting spin structures. Based on the competition among the exchange interactions up to the third neighbor, the system could possibly be pushed into a quantum spin liquid regime by the manipulation of the competing interactions, thereby opening up applications in quantum computing. 17,19 Yet, the Na + ions in the interlayer space of Na 2 IrO 3 lead to disadvantageous interactions between the iridate layers, which interfere with theoretical predictions of a honeycomb arrange-2 ment of spin 1 2 magnetic arrays. 20 Eliminating the interlayer interaction could provide a route to manipulate the spin structure of real materials featuring a spin 1 2 honeycomb arrangement. In RuCl 3 , where no charged ions are in between the honeycomb layers, the interlayer in...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.