Tuning the switching pressure in square lattice coordination networks by metal cation substitution

Coordination networks that undergo guest-induced switching between “closed” nonporous and “open” porous phases are of increasing interest as the resulting stepped sorption isotherms can offer exceptional working capacities for gas storage applications. For practical utility, the gate ad/desorption pressures (Pga/Pgd) must lie between the storage (Pst) and delivery (Pde) pressures and there must be fast switching kinetics. Herein we study the effect of metal cation substitution on the switching pressure of a family of square lattice coordination networks [M(4,4’-bipyridine)2(NCS)]n (sql-1-M-NCS, M = Fe, Co and Ni) with respect to CO2 sorption. The Clausius-Clapeyron equation was used to correlate Pga/Pgd and temperature. At 298 K, Pga/Pgd values were found to vary from 31.6/26.7 bar (M = Fe) to 26.7/20.9 bar (M = Co) and 18.5/14.6 bar (M = Ni). The switching event occurs within 10 minutes as verified by dynamic CO2 sorption tests. In addition, in situ synchrotron PXRD and molecular simulations provided structural insight into the observed switching event, which we attribute to layer expansion of sql-1-M-NCS via intercalation and inclusion of CO2 molecules. This study could pave the way for rational control over Pga/Pgd in switching adsorbent layered materials and enhance their potential utility in gas storage applications.

Reinforcement Learning-Based Routing Protocol to Minimize Channel Switching and Interference for Cognitive Radio Networks

In the existing network-layered architectural stack of Cognitive Radio Ad Hoc Network (CRAHN), channel selection is performed at the Medium Access Control (MAC) layer. However, routing is done on the network layer. Due to this limitation, the Secondary/Unlicensed Users (SUs) need to access the channel information from the MAC layer whenever the channel switching event occurred during the data transmission. This issue delayed the channel selection process during the immediate routing decision for the channel switching event to continue the transmission. In this paper, a protocol is proposed to implement the channel selection decisions at the network layer during the routing process. The decision is based on past and expected future routing decisions of Primary Users (PUs). A learning agent operating in the cross-layer mode of the network-layered architectural stack is implemented in the spectrum mobility manager to pass the channel information to the network layer. This information is originated at the MAC layer. The channel selection is performed on the basis of reinforcement learning algorithms such as No-External Regret Learning, Q-Learning, and Learning Automata. This leads to minimizing the channel switching events and user interferences in the Reinforcement Learning- (RL-) based routing protocol. Simulations are conducted using Cognitive Radio Cognitive Network simulator based on Network Simulator (NS-2). The simulation results showed that the proposed routing protocol performed better than all the other comparative routing protocols in terms of number of channel switching events, average data rate, packet collision, packet loss, and end-to-end delay. The proposed routing protocol implies the improved Quality of Service (QoS) of the delay sensitive and real-time networks such as Cellular and Tele Vision (TV) networks.