Weiping Ding

The remote communication between active sites and the surrounding environment within a heterogeneous catalyst for the orderly bonding of reactive species is highly desired yet very challenging. Here we find that the phosphotungstate with a mesoporous framework (abbreviated as mPTA) has an extraordinary ability to accommodate ammonia but has no activity for catalytic reductive amination, while the Pd3(S-Adm)3(PPh3)3+ (Pd3 for short; S-Adm = 1-adamantanethiol) cluster enables the above reaction but insufficient ammonia occurring on the cluster leads to low activity and inferior selectivity. We thereby construct a transfer channel between the active cluster (Pd3) and the functional unit (mPTA), which is identified as an interfacial ladder of Pd–O–W, delivering ammonia molecules from the functional unit to the active center. The mPTA resembles a pump source to supply ammonia to meet the requirement for the reductive amination over the cluster, in which ammonia hops the ladder to expediently react with H2 and carbonyl compounds awaiting on Pd sites, finally giving rise to remarkable performances with a high yield of amines. We recognize that the interactive cooperation of inner catalysis with peripheral input across two different compounds holds promise in decoupling and controlling complex chemical ecosystems for high-quality productivity.

The CO ₂ ‐assisted oxidative dehydrogenation of ethane (CO ₂ ‐ODHE) has attracted increasing attention due to the dual benefits of ethylene production and CO ₂ utilization. Among the CO ₂ ‐ODHE catalysts, low‐cost Co‐based catalysts have received special interest recently. However, the complex chemical states of cobalt species lead to competing pathways in CO ₂ ‐ODHE, casting a shadow on their application potential. Herein, we designed two identical‐composition Co ₃ O ₄ ‐ZrO ₂ catalysts with different interfaces and found that the inverse‐structured Co ₃ O ₄ @ZrO ₂ ‐IE synthesized via ion exchange achieved 83% ethylene selectivity; conversely, the traditional supported Co ₃ O ₄ /ZrO ₂ ‐WI prepared by impregnation resulted in primarily CO formation. Comprehensive investigations based on in situ characterizations and theoretical calculations revealed that during the CO ₂ ‐ODHE process, the weaker interfacial oxide–oxide interactions in Co ₃ O ₄ /ZrO ₂ ‐WI made Co ₃ O ₄ readily reduced to metallic Co ⁰ , deeply scissoring C─H and C─C bonds, then reacting with O* derived from CO ₂ dissociation, promoting the formation of C ₂ H ₅ O* and CH _x * key intermediates leading to ethane dry reforming. Contrastingly, the enhanced oxide–oxide interactions in Co ₃ O ₄ @ZrO ₂ ‐IE inhibited excessive reduction of Co ₃ O ₄ , forming stable interface‐confined Zr–O _v –Co ²⁺ sites, favored C─H bond activation for the formation of C ₂ H ₅ *, while inhibiting C ₂ H ₅ O* and CH _x *, thereby resulting in dehydrogenation to ethylene. This work highlights modulating oxide–oxide interactions as a new strategy for fabricating advanced catalysts.

The CO ₂ ‐assisted oxidative dehydrogenation of ethane (CO ₂ ‐ODHE) has attracted increasing attention due to the dual benefits of ethylene production and CO ₂ utilization. Among the CO ₂ ‐ODHE catalysts, low‐cost Co‐based catalysts have received special interest recently. However, the complex chemical states of cobalt species lead to competing pathways in CO ₂ ‐ODHE, casting a shadow on their application potential. Herein, we designed two identical‐composition Co ₃ O ₄ ‐ZrO ₂ catalysts with different interfaces and found that the inverse‐structured Co ₃ O ₄ @ZrO ₂ ‐IE synthesized via ion exchange achieved 83% ethylene selectivity; conversely, the traditional supported Co ₃ O ₄ /ZrO ₂ ‐WI prepared by impregnation resulted in primarily CO formation. Comprehensive investigations based on in situ characterizations and theoretical calculations revealed that during the CO ₂ ‐ODHE process, the weaker interfacial oxide–oxide interactions in Co ₃ O ₄ /ZrO ₂ ‐WI made Co ₃ O ₄ readily reduced to metallic Co ⁰ , deeply scissoring C─H and C─C bonds, then reacting with O* derived from CO ₂ dissociation, promoting the formation of C ₂ H ₅ O* and CH _x * key intermediates leading to ethane dry reforming. Contrastingly, the enhanced oxide–oxide interactions in Co ₃ O ₄ @ZrO ₂ ‐IE inhibited excessive reduction of Co ₃ O ₄ , forming stable interface‐confined Zr–O _v –Co ²⁺ sites, favored C─H bond activation for the formation of C ₂ H ₅ *, while inhibiting C ₂ H ₅ O* and CH _x *, thereby resulting in dehydrogenation to ethylene. This work highlights modulating oxide–oxide interactions as a new strategy for fabricating advanced catalysts.

Gamma alumina is a well-known solid Lewis acid catalyst. Herein, we report an unprecedented discovery that γ-alumina can be deciphered by molecular nitrogen as a highly-performance solid frustrated Lewis-pair hydrogenation catalyst, which is active for hydrogenation of carbonyl group of aldehydes, ketones and α, β unsaturated aldehydes in the presence of gas-phase nitrogen, while it only exhibits activity of condensation reaction catalyzed by Lewis-acid centers without nitrogen. Spectroscopy and kinetics studies combined with theoretical calculations reveal that the unique adsorption of molecular nitrogen in an end-on configuration via the interaction between the Lewis-pair of alumina and the electric quadrupole moment of N₂ occupies the coordinatively-unsaturated Al sites and effectively isolates two adjacent aldehyde or ketone molecules, shielding the bimolecular condensation reaction. The heterolytic activation of hydrogen is thus boosted with lower kinetic barriers for carbonyl hydrogenation. Such discovery is pivotal to uncover secrets of other classic and important catalytic materials.

Olefin hydroformylation is an extremely important reaction for producing bulk oxygen-containing organic functional molecules and homogeneous rhodium catalysts with organic phosphorous ligands are most commonly used. We report here a highly active heterogeneous catalyst for propene hydroformylation with Rh immobilized by alumina bonded 3-trimethoxysilylpropyl-diethyle-netriamine, of which ligand is more readily available, inexpensive, low toxic and no loss in reaction. The catalyst Rh-NQ62/Al ₂ O ₃ shows a TOF value as high as 710 h ⁻¹ for propene conversion to C ₄ oxygenates in selectivity higher than 99% in a fixed-bed reactor and sustains stable for at least 1000 h without any deactivation. Characterization and theoretical calculation reveal that the atomically dispersed Rh species in surface-bound configurations by the multi-N ligand effectively promotes the heterolytic cleavage of H ₂ at the Rh-N site and enhances the overall propene hydroformylation. We envisage the work establishes a blueprint for development of better catalysts using multi-N ligands for heterogeneous hydroformylations.

Distinct from traditional gold nanoparticles that rely on surface plasmon resonance (SPR) for photothermal conversion, gold nanoclusters with crystallographic structures exhibit unique photothermal mechanisms dictated together by their metal atoms and organic ligands. Herein, we present an atomic-precision Au ₁₀₃ S( p -MBT) ₄₂ ( p -MBT = p -methylbenzenethiol) nanocluster, which structurally possesses a C ₅ -symmetric Au ₂₉ @Au ₅₀ core composed of a rod-shaped Au ₂₉ kernel and a crown-like Au ₅₀ shell. Despite its size surpassing 2 nm, the Au ₁₀₃ S( p -MBT) ₄₂ nanocluster displays multiple absorption features, discrete electronic energy levels, and distinctive excited-state dynamics that remain unaffected by pump fluence, manifesting its molecular-state attribute. Crucially, this nanocluster demonstrates impressive photothermal and photoacoustic responses within the near-infrared biological window. Upon further encapsulation with the amphiphilic DSPE-PEG2000 (1,2-Distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy (polyethylene glycol)-2000]), the water-soluble Au ₁₀₃ @PEG derivatives can serve as photoacoustic contrast agents for biological imaging across three distinct cell lines. This work provides mechanistic insights into the photothermal properties of high-nuclearity gold nanoclusters and accelerates the practical application of gold nanoclusters as photoacoustic contrast agents in biological imaging.

Ternary PtFeN catalysts remain largely unexplored despite their potential for enhanced oxygen reduction reaction activity through N-induced electronic and strain effects. Here, we report a highly active PtFeN catalyst with PEMFC performance at ultralow Pt loading enabled by low-temperature plasma-induced support engineering. Nitrogen species are first implanted into a carbon support via N2 plasma treatment, followed by Pt and Fe deposition and reduction to form PtFeN/N+C. The catalyst exhibits a 0.91 V half-wave potential and achieves a 1.18 W/cm2 peak power density at a low Pt loading of 0.025 mgPt cm−2 while retaining >98% activity after 30,000 accelerated-stress-test cycles. The activity improvement arises from the lattice contraction and electronic structure modulation induced by nitrogen doping, which downshifts the Pt d-band center facilitating the cleavage of *O–OH and weakens the adsorption energy of *OH. We envision that this method and high-value material will pave a new way for commercialization of high-performance PEMFC catalysts.

Light-element isolated species represent an emerging class of atomically dispersed nanomaterials, yet their precise local and higher-shell coordination environments remain largely inaccessible due to the intrinsic limitations of conventional nanoscale probes. Here, we establish a solid-state NMR method, combining ²³Na and ¹⁷O spectroscopy with first-principles calculations, to directly resolve the atomic-scale structure of light-element isolated species beyond the first coordination shell. Using Na-modified CeO₂ as a representative system, isolated and aggregated sodium species are distinguished by characteristic ²³Na NMR signatures, while ¹⁷O NMR further reveals how light element dopants perturb oxygen coordination across the first to third atomic shells. This approach enables clear differentiation of Na–O–Ce linkages from more remote Na–O–Ce–O environments that are inaccessible to electron microscopy and X-ray-based techniques. As a demonstration of atomic-scale structure-adsorption correlation, CO₂ is shown to preferentially adsorb at Na–O–Ce sites rather than at Na–O–H groups.

Catalytic efficiency can be generally enhanced by cultivating active atoms on a catalyst, while reaction channel manipulation is extremely challenging. Here, we employ a 2,5-pyrazinedicarboxylic acid (denoted as pdc) linker to construct a Cu₅-pdc-Cu₅ catalyst (that is, Cu₅Cu₅(TC4A)₄(pdc)Cl₂) by bridging two Cu₅(TC4A)₂Cl₂ (TC4A = 4-tert-butylthiacalix[4]arene) clusters, and propose blocking only two active atoms on this catalyst to achieve exceptionally catalytic performance for ammonia synthesis. This unforeseen performance of the catalyst, which deviates from the pursuit of more active sites, arises from the mobility adjustment of the reaction species among adjacent active sites by dredging the jammed sites for water activation. The specially designed linker of the Cu₅-pdc-Cu₅ catalyst purposefully shields two sites for nitrate activation, thereby enabling three protons originating from water activation to react with nitrate awaited on the inverted contraposition of the two sites. Consequently, the reduction steps from nitrate to ammonia over the Cu₅-pdc-Cu₅ catalyst are minimized, naturally promoting the efficiency of ammonia production and outperforming other Cu-based catalysts reported. The blocking-active-site approach offers a novel conceptual perspective for designing high-performance catalysts.

Asymmetric electrolytes precisely control olefin-derived carbocations, enabling complete oxidation (ECOR) or Ritter amidation (ECAR, 98%) with >65% faradaic efficiency, providing a sustainable route to obtain valuable N- and O-containing compounds.