![Tailoring memory performance via engineering conjugated bridges in benzo[c][1,2,5]thiadiazole based donor–acceptor small molecules](https://public.readdy.ai/ai/img_res/84d936c0c5dd187c2b9d35f9556f69c9.jpg)
Tuning the conjugated bridges between the electron-donor and electron-acceptor moieties plays a crucial role in enhancing the memristive properties of organic materials, yet it is rarely reported. Herein, we designed and synthesized four donor–acceptor (D-A) organic small molecules, namely 4,7-bis(4-((9H-fluoren-9-ylidene)(phenyl)methyl)phenyl)benzo[c][1,2,5]thiadiazole (DF-BT), 4,7-bis((4-((9H-fluoren-9-ylidene)(phenyl)methyl)phenyl)ethynyl)benzo[c][1,2,5]thiadiazole (DF-ynl-BT), 4,7-bis(5-(4-((9H-fluoren-9-ylidene)(phenyl)methyl)phenyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DF-Th-BT), and 4,7-bis((5-(4-((9H-fluoren-9-ylidene)(phenyl)methyl)phenyl)thiophen-2-yl)ethynyl)benzo[c][1,2,5]thiadiazole (DF-Th-ynl-BT), featuring unique conjugated bridges. These molecules were employed as active layers in resistive random-access memory (RRAM) devices to systematically investigate the influence of conjugation bridges on the electrical parameters. The results revealed that devices based on DF-BT, DF-ynl-BT, and DF-Th-BT exhibited write-once-read-many-times (WORM) characteristics, while the DF-Th-ynl-BT-based device demonstrated stable Flash-type switching behavior. Compared to DF-BT, memory devices utilizing DF-ynl-BT, DF-Th-BT, and DF-Th-ynl-BT, which incorporate additional conjugated bridges, exhibited nonvolatile memory properties with reduced threshold voltages, an improved ON/OFF current ratio, enhanced stability, and better uniformity. These findings demonstrated that tailoring the conjugated bridges in D-A molecules can effectively modulate resistive memory behavior and enhance device performance. Furthermore, the DF-Th-ynl-BT-based device was successfully integrated into logic gate circuits and display functions, highlighting its significant potential for applications in artificial intelligence (AI) neural networks.
Methanol steam reforming (MSR) is a promising technology for in situ hydrogen production, while the mechanistic role of zinc in the widely used Cu/ZnO/Al2O3 catalyst remains ambiguous. Electronic metal–support interactions (EMSIs) are generally applied for modulating active sites in such heterogeneous catalysts, offering opportunities to optimize energy conversion processes. Here, we revealed that a dynamic EMSI between Cu and ZnO enhances catalytic performance by constructing ZnOx/Cu interfaces, facilitating bidirectional electron transfer between ZnOx and Cu. The electron transfer from ZnOx to Cu mitigates overoxidation of Cu0 to Cu+ during water activation, thereby improving water activation efficiency, while the electron transfer back to ZnOx accelerates the reduction of Cu+ back to Cu0, promoting dehydrogenation of reactive formate at the ZnOx/Cu interface, the rate-determining step at low temperatures. Thus, we establish a dual role for the EMSI-induced ZnOx/Cu interface in stabilizing active intermediates and facilitating redox cycling. These findings provide insights into the precise regulation of catalytic active sites via EMSI engineering, offering guidance for high-efficiency catalysts design for sustainable energy conversion.
In article number 2002094, Yuxin Tang, Yuekun Lai, Xiaodong Chen, and co‐workers report a mechanically reinforced localized structure with ultralong titania nanotubes to alleviate the mechanical strain and stabilize the solid–electrolyte interface layer for silicon‐based anode materials, delivering low electrode thickness swelling and excellent cycling performance.
Regulating the vertical composition distribution of an organic electronic donor and acceptor is an effective strategy for the fabrication of high-performance organic photodetectors (OPDs). In this study, after the one-step solution process to fabricate an active layer, an ultrasonic-assisted solvent vapor annealing method (UA-SVA) was proposed to modulate the vertical distribution of the PBDB-T:ITIC BHJ layer in an OPD device. Compared to the control device processed from SVA, the obtained OPD from UA-SVA exhibits both a decreased dark current and slightly enhanced photocurrent. As a result, the photodetectivity of the device treated by UA-SVA was more than one order of magnitude higher than that of the control counterpart in the detective spectrum ranging from 450 to 750 nm. Especially, a dramatically high photodetectivity of 2.17 × 1012 Jones at a wavelength of 688 nm has been achieved under a reverse bias of −0.5 V. To illuminate the reason for OPD performance improvement, ultraviolet–visible (UV–vis) absorption spectroscopy, space-charge-limited current (SCLC) method, atomic force microscopy (AFM), and water contact angle (WCA) measurement were performed, and the enhanced light-absorption intensity, improved charge carrier transport efficiency, and the modified interfacial contact and surface morphology of the BHJ active layer were observed.
Hydrogen is an ideal energy carrier and plays a critical role in the future energy transition. Distinct from steam reforming, electrochemical water splitting, especially powered by renewables, has been considered as a promising technique for scalable production of high-purity hydrogen with no carbon emission. Its commercialization relies on the reduction of electricity consumption and thus hydrogen cost, calling for highly efficient and cost-effective electrocatalysts with the capability of steadily working at high hydrogen output. This requires the electrocatalysts to feature (1) highly active intrinsic sites, (2) abundant accessible active sites, (3) effective electron and mass transfer, (4) high chemical and structural durability, and (5) low-cost and scalable synthesis. It should be noted that all these requirements should be fulfilled together for a practicable electrocatalyst. Much effort has been devoted to addressing one or a few aspects, especially improving the electrocatalytic activity by electronic modulation of active sites, while few reviews have focused on the synergistic modulation of these aspects together although it is essential for advanced electrochemical water splitting. In this Account, we will present recent innovative strategies with an emphasis on our solutions for synergistically modulating intrinsic active sites, electron transportation, mass transfer, and gas evolution, as well as mechanical and chemical durability, of non-precious-metal electrocatalysts, aiming for cost-effective and highly efficient water splitting. The following approaches for coupling these aspects are summarized for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER). (1) Synergistic electronic modulations. The electronic structure of a catalytic site determines the adsorption/desorption of reactive intermediates and thus intrinsic activity. It can be tuned by heterogeneous doping, strain effect, spin polarization, etc. Coupling these effects to optimize the reaction pathways or target simultaneously the activity and stability would advance electrocatalytic performance. (2) Synergistic electronic and crystalline modulation. The crystallinity, crystalline phase, crystalline facets, crystalline defects, etc. affect both activity and stability. Coupling these effects with electronic modulation would enhance the activity together with stability. (3) Synergistic electronic and morphological modulation. It will focus on concurrently modulating electronic structure for improving the intrinsic activity and morphology for increasing accessible active sites, especially through single action or processing. The mass transfer and gas evolution properties can also be enhanced by morphological modulation to enable water splitting at large output. (4) Synergistic modulation of elementary reactions. Electrocatalytic reaction generally consists of a couple of elementary reactions. Each one may need a specific active site. Designing and combining various components targeting every elementary step on a space-limited catalyst surface will balance the intermediates and these steps for accelerating the overall reaction. (5) Integrated electrocatalyst design. Taking all these strategies together into account is necessary to integrate all above essential features into one electrocatalyst for enabling high-output water electrolysis. Beyond the progress made to date, the remaining challenges and opportunities is also discussed. With these insights, hopefully, this Account will shed light on the rational design of practical water-splitting electrocatalysts for the cost-effective and scalable production of hydrogen.
In article number 2001073, Hong Meng, Feng Yan, and co‐workers design, synthesize, and successfully use a non‐fullerene electron transport material based on a new spiro derivative, SPS‐4F, in perovskite solar cells, leading to high efficiency as well as good stability of the devices. This work opens a new avenue for developing new spiro‐based electron transport materials and paves a way for realizing high‐performance devices at low costs.
In article number 1908176, Joshua D. Caldwell, Alexey Y. Nikitin, Pablo Alonso‐González, and co‐workers extract the IR permittivity of the biaxial crystal α‐MoO3 by correlative far‐ and near‐field measurements, using FTIR reflectance spectroscopy and s‐SNOM polariton interferometry, thus providing both an accurate permittivity model and a novel approach to extracting dielectric functions of nanomaterials. Moreover, through density functional theory, insights into the vibrational states dictating such permittivity are revealed.