On the basis of the unique chaotropic supramolecular assembly of cucurbit[5]­uril (CB5) and dodecahydro-closo-dodecaborate anion [closo-B12H12]2–, we have developed an efficient and universal platform to fabricate shape-controlled dodecaborate-based supramolecular organic frameworks (BOFs) decorated with ultrafine monodispersed trimetallic alloys. Simply by regulating the molar ratio of CB5 and [closo-B12H12]2–, a series of fascinating morphologies, such as flowerlike structures, nanorods, nanocubes, and nanosheets, were successfully constructed. These obtained BOFs were proved to be good substrate supports for in situ synthesis of trimetallic PtCoNi nanoalloys, where the final PtCoNi–BOFs materials were obtained efficiently as a precipitate from aqueous solutions, and showed excellent catalytic performance in ammonia borane hydrolysis with a high turnover frequency of 1490 molH2 molPt –1 min–1 and a low activation energy of 15.79 kJ mol–1.

CO2 reduction to carbon feedstocks using heterogeneous photocatalysis technique has been deemed as an attractive means of addressing both deteriorating greenhouse effect and depletion of fossil fuels. Nevertheless, deficiency of accessible active sites on the catalyst surface, low CO2 adsorption rate, and short carrier lifetime retard the photocatalytic CO2 conversion into hydrocarbon fuels. In this study, the controllable construction of spatially separated directional charge transport pathways over multilayered heterostructured transition metal chalcogenides (TMCs) based photosystems for high‐performance photocatalytic CO2‐to‐syngas conversion are shown. In this scenario, ultrathin non‐conjugated insulating poly(diallyl‐dimethyl‐ammonium chloride) (PDDA) layer are intercalated in‐between TMCs and layered double hydroxide (LDH) and serve as an efficient electron transfer mediator, whilst LDH functions as a hole‐withdrawing regulator, both of which synergistically foster the spatial vectorial charge migration/separation over TMCs, thus endowing the TMCs/PDDA/LDH heterostructures with significantly boosted visible‐light‐driven photoactivity toward CO2 conversion into syngas. This study can inspire sparkling new ideas to realize fine tuning of charge motion for stimulating solar‐to‐fuel conversion.

Atomically precise metal nanoclusters (NCs) have recently emerged as a pivotal sector of metal nanomaterials due to unique atomic stacking mode, quantum confinement effect and abundant catalytically active sites. In...

Organic polymers have attracted much attention in the field of energy conversion owing to their excellent tailoring ability via heterometal incorporation and/or functionalization. Herein, a novel pincer complexbridged porphyrin polymer is synthesized using Cu-porphyrin (CuPor) and Ru-N′NN′-pincer complex (RuN 3 ) as monomers. The resultant CuPor-RuN 3 polymer delivers robust electrocatalytic hydrogen evolution reaction (HER) performance with outstanding durability and ultralow overpotentials of 73 and 114 mV at a current density of 10 mA cm -2 in acidic and alkaline media, respectively. Moreover, the CuPor-RuN 3 polymer displays great potential to fabricate photoelectrochemical (PEC) cells with a BiVO 4 photoanode, where the additional photoinduced electrons from CuPor-RuN 3 endow the BiVO 4 ||CuPor-RuN 3 PEC cell with much better activity for overall water splitting than the BiVO 4 ||Pt/C one, demonstrating that CuPor-RuN 3 would be a promising (photo)electrocatalyst to replace the benchmark Pt/C. The experimental and theoretical studies reveal that the Cu/Ru heterobimetallic centers in the polymer not only enhance the inherent electron transfer from Cu sites to Ru ones that serve as singleatom catalytic sites (Ru-N 3 ), but also efficiently regulate the electronic property of the Ru-N 3 sites, and thus boosting (photo)electrocatalytic HER activity. The proposed strategy opens a new avenue to fabricate porphyrinbased polymers with heteromultimetallic centers as effective HER (photo)electrocatalysts.

The rational design of the directional charge transfer channel represents an important strategy to finely tune the charge migration and separation in photocatalytic CO2‐to‐fuel conversion. Despite the progress made in crafting high‐performance photocatalysts, developing elegant photosystems with precisely modulated interfacial charge transfer feature remains a grand challenge. Here, a facile one‐pot method is developed to achieve in situ self‐assembly of Pd nanocrystals (NYs) on the transition metal chalcogenide (TMC) substrate with the aid of a non‐conjugated insulating polymer, i.e., branched polyethylenimine (bPEI), for photoreduction of CO2 to syngas (CO/H2). The generic reducing capability of the abundant amine groups grafted on the molecular backbone of bPEI fosters the homogeneous growth of Pd NYs on the TMC framework. Intriguingly, the self‐assembled TMCs@bPEI@Pd heterostructure with bi‐directional spatial charge transport pathways exhibit significantly boosted photoactivity toward CO2‐to‐syngas conversion under visible light irradiation, wherein bPEI serves as an efficient hole transfer mediator, and simultaneously Pd NYs act as an electron‐withdrawing modulator for accelerating spatially vectorial charge separation. Furthermore, in‐depth understanding of the in situ formed intermediates during the CO2 photoreduction process are exquisitely probed. This work provides a quintessential paradigm for in situ construction of multi‐component heterojunction photosystem for solar‐to‐fuel energy conversion.

Metal nanoclusters (NCs) have been unleashed as an emerging category of metal materials by virtue of integrated merits including the unusual atom-stacking mode, quantum confinement effect, and fruitful catalytically active sites. Nonetheless, development of metal NCs as photosensitizers is blocked by light-induced instability and ultrashort carrier lifespan, which remarkably retards the design of metal NC-involved photosystems, hence resulting in the decreased photoactivities. To solve these obstacles, herein, we conceptually probed the charge transfer characteristics of the BiVO 4 photoanode photosensitized by atomically precise alloy metal NCs, wherein tailor-made Lglutathione-capped gold-silver bimetallic (AuAg) NCs were controllably self-assembled on the BiVO 4 substrate. It was uncovered that alien Ag atom doping is able to effectively stabilize the alloy AuAg NCs and simultaneously photosensitize the BiVO 4 photoanode, significantly boosting the photoelectrochemical (PEC) water oxidation performances. The reasons for the robust and stable PEC water oxidation activities of the AuAg NCs/BiVO 4 composite photoanode were unambiguously unleashed. We ascertain that Ag atom doping in the staple motif of Au x NCs efficaciously protects the NCs from rapid oxidation, enhancing the photostability, boosting the photosensitization efficiency, and thus leading to the considerably improved PEC water splitting activities compared with the homometallic counterpart. This work could afford a new strategy to judiciously tackle the inherent detrimental instability of metal NCs for solar energy conversion.

Transition-metal chalcogenides (TMCs) have received enormous attention by virtue of their large light absorption coefficient, abundant catalytically active sites, and markedly reduced spatially vectorial charge-transfer distance originating from generic structural merits. However, the controllable construction of TMC-based heterostructured photosystems for photocatalytic carbon dioxide (CO2) reduction is retarded by the ultrashort charge lifetime, sluggish charge-transfer kinetics, and low target product selectivity. Herein, we present the rational design of two-dimensional (2D)/zero-dimensional (0D) heterostructured CO2 reduction photosystems by an electrostatic self-assembly strategy, which is enabled by precisely anchoring CsPbBr3 quantum dots (QDs) on the 2D TMC (CdIn2S4, ZnIn2S4, In2S3) frameworks. The peculiar 2D/0D integration mode and suitable energy-level alignment between these two assembly units afford maximal interfacial contact and applicable potential for CO2 photoreduction, thus endowing the self-assembled TMCs/CsPbBr3 nanocomposites with considerably improved visible-light-driven photocatalytic performances toward CO2 reduction to carbon monoxide with high selectivity. The enhanced photocatalytic performances of TMCs/CsPbBr3 heterostructures are attributed to the abundant active sites on the TMC frameworks, excellent light absorption of CsPbBr3 QDs, and well-defined 2D/0D heterostructures of TMCs/CsPbBr3 QDs photosystems, which synergistically boosts the directional charge transport from CsPbBr3 QDs to TMCs, enhancing the interfacial charge migration/separation. Our work would inspire the construction of novel TMCs-involved photosystems for solar-to-fuel conversion.

Using in situ reduction strategy by combining organic frameworks and ultrafine Pd and Pt nanoparticles (PdÀ NPs and PtÀ NPs) to synthesize composites with tunable morphology and high dispersion has attracted extensive attentions in fabrication of composite nanomaterials. Herein, on the new kind of substrate, BOPs@Pd and BOPs@Pt nano materials have been successfully fabricated via in situ reduction of Na 2 PdCl 4 and H 2 PtCl 6 triggered by reducibility of organic boron polymers (BOPs). The final products are obtained by loading PdÀ NPs and PtÀ NPs with ultra-small size and high dispersion without any tedious chemical modification or additional additives. These materials show high catalytic activity and recyclability in the hydrolysis dehydrogenation of ammonia borane (AB).(kJ · mol À 1 ), T is the absolute temperature (K), and R is gas constant (8.314 J · K À 1 · mol À 1 ).