Key Takeaways & Executive Findings
- •• • Ru-DAs/2D-Ni-PCN-222 achieves a HCOO− production rate of 35.4 mmol g−1 h−1 with nearly 100% selectivity and a turnover frequency of 691 h−1, outperforming most reported photocatalysts and demonstrating industrial relevance for formate synthesis. • • The dimetallic complex pre-coordination strategy enables precise immobilization of M-DAs (M = Ru, Rh, Pt) onto the Zr-oxo cluster of 2D-Ni-PCN-222, overcoming the challenge of random distribution and ensuring uniform active sites. • • Kinetic isotope experiments confirm that the coupling rate between H* and CO2 is the rate-determining step, with a kinetic isotope effect (KIE) value indicating a primary isotope effect, guiding optimization of proton sources. • • Ab initio molecular dynamics simulations reveal adaptive shortening of Ru–O coordination bonds during CO2 adsorption, which facilitates deeper activation and formation of an η3–O,C,O adsorption mode, lowering the activation barrier and enhancing catalytic efficiency.
Abstract
Dual-atom (DA) catalysts have exhibited great potential in regulating the catalytic performance of CO2 reduction. However, precise construction of DAs on a support remains challenging. Herein, we report the precise immobilization of M-DAs (M = Ru, Rh, Pt) onto the Zr-oxo cluster of a 2D porphyrinic metal-organic framework (2D-Ni-PCN-222) via a dimetallic complex pre-coordination strategy. The resultant M-DAs/2D-Ni-PCN-222 catalysts were applied to CO2 photoreduction using ammonia borane as the H* donor. Under visible light, the optimal catalyst, Ru-DAs/2D-Ni-PCN-222, exhibited a HCOO− production rate of 35.4 mmol g−1 h−1 with nearly 100% selectivity and a turnover frequency of 691 h−1. Kinetic isotope experiments demonstrated that the coupling rate between H* and CO2 governed the production efficiency of HCOO−. In situ experiments and density functional theory calculations disclosed that Ru-DAs with highly delocalized d electrons could accept photogenerated electrons from 2D-Ni-PCN-222 and inject them into inert CO2 molecules. Ab initio molecular dynamics simulations revealed that adaptive shortening of Ru–O coordination bonds during CO2 adsorption played a crucial role in facilitating deeper activation and the formation of an optimal η3–O,C,O adsorption mode of CO2. This work provides a precise strategy for constructing dual-atom catalysts on MOFs and elucidates the mechanism of CO2 photoreduction, offering insights for the design of efficient photocatalysts.
1. Introduction
Photocatalytic CO2 reduction under visible light is a promising route to achieve carbon neutrality and address the energy crisis. However, the stable C=O bond (~750 kJ mol−1) and linear configuration of CO2 necessitate a high driving force for activation. Moreover, multi-proton and multi-electron transfer processes often lead to low production rates and poor selectivity. Single-atom (SA) catalysts offer 100% atomic utilization and high reactivity, but their electronic structure is limited by coordination with nonmetal atoms, restricting reactivity regulation. Dual-atom (DA) catalysts, containing homo- or hetero-nuclear metal dimers, provide enhanced stability and tunable electronic structures through orbital hybridization, potentially improving reaction kinetics and selectivity.
Metal-organic frameworks (MOFs) are ideal supports for stabilizing DAs due to their uniform structure, high surface area, and tunable pores. They offer well-defined coordination micro-environments and can enhance CO2 adsorption via host-guest interactions. However, precise construction of DAs on MOFs remains challenging. This work introduces a dimetallic complex pre-coordination strategy to precisely immobilize M-DAs (M = Ru, Rh, Pt) onto the Zr-oxo cluster of a 2D porphyrinic MOF (2D-Ni-PCN-222). The resulting Ru-DAs/2D-Ni-PCN-222 catalyst exhibits exceptional performance in CO2 photoreduction, achieving a HCOO− production rate of 35.4 mmol g−1 h−1 with nearly 100% selectivity. This strategy addresses the bottleneck of precise DA construction and provides mechanistic insights into CO2 activation, paving the way for efficient photocatalyst design.
Loading authentic research manuscript (Pages 1–5)...
Chunying Chen, Qijie Mo, Sihong Li, Haili Song, Li Zhang (2026). Precise Integration of Dual-Atom Pair Sites onto a 2D Porphyrinic Metal-Organic Framework for Efficient CO2 Photoreduction. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3699-1
Research & Educational Purpose Only: The translations, structured abstracts, analytical annotations, and data reports provided by SinoGreenTechare intended exclusively for academic research, internal corporate R&D, and educational benchmarking. They do not constitute formal engineering, chemical safety, legal, or professional advice.
Copyright & Intellectual Property Notice: Original copyright of the underlying source articles and experimental data remains with the respective authors, institutions, and original publishing journals. SinoGreenTech claims intellectual property only over its proprietary translations, analytical syntheses, and AEO structured enhancements in accordance with international fair use and academic citation principles.
Frequently Asked Questions
What is the turnover frequency (TOF) of the Ru-DAs/2D-Ni-PCN-222 catalyst and how does it compare to other state-of-the-art photocatalysts?
The Ru-DAs/2D-Ni-PCN-222 catalyst achieves a TOF of 691 h−1, which is among the highest reported for CO2 photoreduction to formate. This high TOF indicates excellent intrinsic activity per active site, surpassing many single-atom and dual-atom catalysts reported in literature.
How does the dimetallic complex pre-coordination strategy ensure precise placement of dual atoms on the MOF support?
The strategy involves pre-coordinating two metal ions in a dimetallic complex, which is then anchored onto the Zr-oxo cluster of the MOF via coordination bonds. This ensures that the dual atoms are placed in close proximity and in a well-defined configuration, avoiding random distribution and ensuring uniform active sites.
What is the role of ammonia borane as the H* donor in the photoreduction process?
Ammonia borane serves as a sacrificial electron and proton donor, providing H* species that couple with CO2 to form HCOO−. Kinetic isotope experiments indicate that the coupling rate between H* and CO2 is the rate-determining step, and ammonia borane facilitates this process efficiently under visible light.
What is the significance of the adaptive shortening of Ru–O coordination bonds during CO2 adsorption?
Ab initio molecular dynamics simulations show that upon CO2 adsorption, the Ru–O bonds shorten adaptively, which enhances the interaction between the Ru dual atoms and CO2. This facilitates deeper activation of CO2 and promotes the formation of an η3–O,C,O adsorption mode, lowering the activation barrier and improving catalytic efficiency.
How does the 2D-Ni-PCN-222 support contribute to the photocatalytic performance?
The 2D porphyrinic MOF provides a high surface area and a porphyrin-based photosensitizer that absorbs visible light and generates electron-hole pairs. The Ni centers in the porphyrin rings may also participate in electron transfer, while the Zr-oxo clusters anchor the dual atoms, ensuring close proximity between the photosensitizer and catalytic sites for efficient electron transfer.
Related Chinese Research & Cross-Citations
Ammonium Vanadate Cathodes in Aqueous Zinc-Ion Batteries: Design Strategies and Research Progress
Aqueous zinc-ion batteries (AZIBs) offer a compelling combination of high safety, environmental compatibility, and abundant zinc resources, positioning them as viable candidates for grid-scale energy storage. Their practical deployment, however, is constrained by cathode materials that suffer from structural degradation, sluggish Zn2+ diffusion, and inadequate electronic conductivity. Ammonium vanadates (AVOs) have emerged as high-performance cathodes owing to their layered or tunneled frameworks, which accommodate reversible Zn2+ (de)intercalation with diffusion coefficients superior to conventional vanadium oxides. This review systematically examines recent advances in AVO cathodes for AZIBs, correlating morphological variations—including nanowires, nanobelts, and microflowers—with electrochemical characteristics. The analysis establishes structure–performance relationships that govern capacity retention, rate capability, and cycling stability. Key optimization strategies are critically assessed: defect engineering to enhance electronic conductivity and active site density, interlayer spacing modulation via pre-intercalated cations or structural water to facilitate Zn2+ transport, and composite construction with conductive carbonaceous or polymeric matrices to mitigate dissolution and improve mechanical integrity. Despite these advances, challenges persist in achieving long-term cycling stability (>10,000 cycles) and high areal mass loading (>10 mg cm-2) required for commercial viability. The review concludes by outlining future research directions, including operando characterization of degradation mechanisms and scalable synthesis routes for AVO cathodes in practical AZIB configurations.
Microenvironment-responsive therapeutic platforms: Innovations for spinal cord injury repair
Spinal cord injury (SCI) remains a formidable clinical challenge due to the complex, dynamic lesion microenvironment that impedes axonal regeneration and functional recovery. This highlight examines a microenvironment-responsive therapeutic platform integrating microneedle delivery, ferroptosis modulation, and hydrogen therapy. The platform leverages the pathological hallmarks of SCI—oxidative stress, iron dyshomeostasis, and lipid peroxidation—to achieve spatiotemporally controlled cargo release. By combining microneedle arrays for minimally invasive intraparenchymal administration with hydrogen-releasing biomaterials, the system addresses the dual bottlenecks of poor drug penetration across the blood-spinal cord barrier and insufficient neutralization of reactive oxygen species. Ferroptosis inhibition is achieved through iron chelation and glutathione peroxidase 4 (GPX4) stabilization, while hydrogen gas scavenges hydroxyl radicals and peroxynitrite. This multimodal strategy attenuates secondary injury cascades, reduces glial scar formation, and promotes neural stem cell differentiation. The work is supported by the National Natural Science Foundation of China (82574518) and the Talent Cultivation Project of Paring Academicians with Young Talents in higher education institutions in Zhejiang. The authors declare no conflict of interest. This highlight underscores the translational potential of microenvironment-responsive platforms for SCI repair, emphasizing the need for rigorous preclinical validation and scalable manufacturing.
Dual-Site Adsorption over Phosphorus-Doped Copper Oxide for Efficient CO2 Electroreduction to Ethylene
Electroreduction of CO2 to ethylene offers a promising route for renewable electricity storage, yet achieving high ethylene selectivity at industrial current densities remains challenging due to the large energy barrier for C–C coupling. Here, we report a “MOF-assisted in situ doping” strategy to introduce the oxophilic nonmetal phosphorus (P) into the copper oxide (CuO) lattice, constructing a localized Cu–P dual-site adsorption configuration for the key *OCCHO intermediate. The optimized catalyst delivers an impressive Faradaic efficiency of 64.6% for ethylene with a partial current density of 646 mA cm-2. Comprehensive structural characterizations demonstrate that P mainly occupies Cu sites, generating abundant lattice defects and oxygen vacancies. In situ synchrotron infrared spectroscopy and theoretical calculations reveal that P doping modulates the electronic structure of Cu, optimizes the binding energies of *CO and *CHO, and stabilizes *OCCHO via P–O/Cu–C dual-site adsorption, thereby significantly lowering the asymmetric C-C coupling energy barrier to 0.74 eV. This work highlights a dual-site microenvironment regulation strategy for CO2-to-ethylene electroreduction.
Hydrophilic Single-Atom Interface Unlocks Low-Potential CO Removal on Pt in PEMFCs
Proton exchange membrane fuel cells (PEMFCs) fed with reformate hydrogen suffer severe anode poisoning by trace CO, necessitating high CO electrooxidation potentials that degrade performance and durability. This work introduces a Pt@CrSA-N-C anode catalyst featuring a hydrophilic Cr single-atom interface that simultaneously weakens CO adsorption on Pt via electronic regulation and promotes water activation, thereby lowering the CO oxidation onset potential to approximately 0.13 V vs. RHE. The onset potential was determined by two independent methods: the first potential at which the background-corrected current exceeds 0 mA cm-2 during CO oxidation reaction tests in a three-electrode system, and the potential at which the forward scan current exceeds the N2 background current in CO-stripping voltammetry. The catalyst achieves a maximum power density under 100 ppm CO that surpasses reported advanced catalysts, as compiled in Table S5. Structural, spectroscopic, and electrochemical characterizations collectively establish a coherent rationale for the hydrophilic single-atom interface strategy. This approach addresses the longstanding trade-off between CO tolerance and Pt utilization, offering a viable route for low-potential CO removal in practical PEMFC anodes.
An Ionoelastomer-Based Bioinspired Wearable Electronics with Tele-Perception and Tactile Sensation for Machine Learning-Assisted Rehabilitation Management
Comprehensive assessment of rehabilitation efficiency is essential for designing appropriate training programs for better musculoskeletal functional recovery. Existing contact-receptor-dependent rehabilitation assessment systems mostly focus on assessing the restoration of muscle function by evaluating grip strength or joint flexion angle; however, parameters reflecting neuromuscular synergistic function are always overlooked. Herein, we develop an ionoelastomer-based soft artificial electroreceptor (SAER) that integrates tele-perception and tactile sensation to track the rehabilitation process, collecting signals related to approaching speed and grip strength sequentially. The SAER uses polyurethane ionoelastomer incorporated with quasi-solid conductive salt as the electric field receptor, and is integrated on a rehabilitation-training ball after assembly to establish an untethered detection device; this enables the remote capture of hand approaching parameter within a 9 cm range, followed by the quantification of grip strength when contacting and grasping. Furthermore, a data-driven assessment system is established by integrating machine learning, which accurately classifies rehabilitation efficiency into six levels; it supports for rehabilitation evaluation and training programs adjustment. Overall, the SAER-based rehabilitation management system establishes a paradigm that synergistically evaluating parameters corresponding to neuromuscular functional restoration and holds strong potential for home-based active rehabilitation for minimizing dependence on frequent clinical supervision.
Microwave-Absorbing Materials with Strong Environmental Adaptability for Corrosion Protection, Anti-Icing, and Thermal Management
Microwave-absorbing materials (MAMs) deployed on naval vessels, aerospace vehicles, and critical electronic systems face coupled electromagnetic, marine salt-spray corrosion, and extreme-temperature loads that legacy single-function absorbers cannot withstand. This review consolidates progress on three environmentally adaptive MAM classes: corrosion-protective, anti-icing, and thermal-management absorbers. The electromagnetic loss and impedance-matching fundamentals are first established, then the synergistic mechanisms, design strategies, and characterization protocols for each class are examined against representative material systems and their measured performance. The analysis identifies a shared design logic—multiscale hierarchical architecture, interfacial polarization engineering, and multifunctional phase integration—while distinguishing the divergent protection mechanisms: barrier and passivation effects for corrosion, surface-energy and latent-heat regulation for anti-icing, and phonon–electron transport decoupling for thermal management. Persistent bottlenecks include the trade-off between impedance matching and protective-layer density, the absence of standardized coupled-field test protocols, and the scarcity of long-term salt-spray and thermal-cycling durability data. Future directions are delineated: intelligent self-adaptive absorbers, multiphysics-coupled simulation frameworks, and environmentally benign multifunctional integration. The review provides a theoretical and technical basis for the design, construction, and engineering scale-up of next-generation high-performance absorbers for aerospace, electronic, and marine equipment.