Stable Interfacial Ruthenium Species for Highly Efficient Polyolefin Upcycling.

The present polyolefin hydrogenolysis recycling cases acknowledge that zerovalent Ru exhibits high catalytic activity. A pivotal rationale behind this assertion lies in the propensity of the majority of Ru species to undergo reduction to zerovalent Ru within the hydrogenolysis milieu. Nonetheless, the suitability of zerovalent Ru as an optimal structural configuration for accommodating multiple elementary reactions remains ambiguous. Here, we have constructed stable Ru0-Ruδ+ complex species, even under reaction conditions, through surface ligand engineering of commercially available Ru/C catalysts. Our findings unequivocally demonstrate that surface-ligated Ru species can be stabilized in the form of a Ruδ+ state, which, in turn, engenders a perturbation of the σ bond electron distribution within the polyolefin carbon chain, ultimately boosting the rate-determining step of C-C scission. The optimized catalysts reach a solid conversion rate of 609 g·gRu-1·h-1 for polyethylene. This achievement represents a 4.18-fold enhancement relative to the pristine Ru/C catalyst while concurrently preserving a remarkable 94% selectivity toward valued liquid alkanes. Of utmost significance, this surface ligand engineering can be extended to the gentle mixing of catalysts in ligand solution at room temperature, thus rendering it amenable for swift integration into industrial processes involving polyolefin degradation.

Layered Double Hydroxide Derivatives for Polyolefin Upcycling.

While Ru-catalyzed hydrogenolysis holds significant promise in converting waste polyolefins into value-added alkane fuels, a major constraint is the high cost of noble metal catalysts. In this work, we propose, for the first time, that Co-based catalysts derived from CoAl-layered double hydroxide (LDH) are alternatives for efficient polyolefin hydrogenolysis. Leveraging the chemical flexibility of the LDH platform, we reveal that metallic Co species serve as highly efficient active sites for polyolefin hydrogenolysis. Furthermore, we introduced Ni into the Co framework to tackle the issue of restricted hydrogenation ability associated with contiguous Co-Co sites. In-situ analysis indicates that the integration of Ni induces electron transfer and facilitates hydrogen spillover. This dual effect synergistically enhances the hydrogenation/desorption of olefin intermediates, resulting in a significant reduction in the yield of low-value CH4 from 27.1 to 12.6%. Through leveraging the unique properties of LDH, we have developed efficient and cost-effective catalysts for the sustainable recycling and valorization of waste polyolefin materials.

Insights on the stem elongation of spur-type bud sport mutant of 'Red Delicious' apple.

MAIN CONCLUSION: The decreased capacity of auxin-, CTK-, and BR-mediated cell division and cell enlargement pathways, combined with the enhanced capacity of GA and ETH-, JA-, ABA-, SA-mediated stress-resistant pathways were presumed to be the crucial reasons for the formation of spur-type 'Red Delicious' mutants. Vallee Spur', which exhibit short internodes and compact tree shape, is the fourth generation of the spur-type bud sport mutant of 'Red Delicious'. However, the underlying molecular mechanism of these properties remains unclear. Here, comparative phenotypic, full-length transcriptome and phytohormone analyses were performed between 'Red Delicious' (NSP) and 'Vallee Spur' (SP). The new shoot internode length of NSP was ˃ 1.53-fold higher than that of the SP mutant. Cytological analysis showed that the stem cells of the SP mutant were smaller and more tightly arranged relative to the NSP. By Iso-Seq, a total of 1426 differentially expressed genes (DEGs) were detected, including 808 upregulated and 618 downregulated genes in new shoot apex with 2 leaves of the SP mutant. Gene expressions involved in auxin, cytokinin (CTK), and brassinosteroid (BR) signal transduction were mostly downregulated in the SP mutant, whereas those involved in gibberellin (GA), ethylene (ETH), jasmonate (JA), ABA, and salicylic acid (SA) signal transduction were mostly upregulated. The overall thermogram analysis of hormone levels in the shoot apex carrying two leaves detected by LC-MS/MS absolute quantification showed that the levels of IAA-Asp, IAA, iP7G, OPDA, and 6-deoxyCS were significantly upregulated in the SP mutant, while the remaining 28 hormones were significantly downregulated. It is speculated that the decreased capacity of auxin, CTK, and BR-mediated cell division and cell enlargement pathways is crucial for the formation of the SP mutant. GA and stress-resistant pathways of ETH, JA, ABA, and SA also play vital roles in stem elongation. These results highlight the involvement of phytohormones in the formation of stem elongation occurring in 'Red Delicious' spur-type bud sport mutants and provide information for exploring its biological mechanism.

Genome-Wide Identification and Analysis of the Genes Encoding Q-Type C2H2 Zinc Finger Proteins in Grapevine.

Q-type C2H2 zinc finger proteins (ZFPs), the largest family of transcription factors, have been extensively studied in plant genomes. However, the genes encoding this transcription factor family have not been explored in grapevine genomes. Therefore, in this study, we conducted a genome-wide identification of ZFP genes in three species of grapevine, namely Vitis vinifera, Vitis riparia, and Vitis amurensis, based on the sequence databases and phylogenetic and their conserved domains. We identified 52, 54, and 55 members of Q-type C2H2 ZFPs in V. vinifera, V. riparia, and V. amurensis, respectively. The physical and chemical properties of VvZFPs, VrZFPs, and VaZFPs were examined. The results showed that these proteins exhibited differences in the physical and chemical properties and that they all were hydrophobic proteins; the instability index showed that the four proteins were stable. The subcellular location of the ZFPs in the grapevine was predicted mainly in the nucleus. The phylogenetic tree analysis of the amino acid sequences of VvZFP, VaZFP, VrZFP, and AtZFP proteins showed that they were closely related and were divided into six subgroups. Chromosome mapping analysis showed that VvZFPs, VrZFPs, and VaZFPs were unevenly distributed on different chromosomes. The clustered gene analysis showed that the motif distribution was similar and the sequence of genes was highly conserved. Exon and intron structure analysis showed that 118 genes of ZFPs were intron deletion types, and the remaining genes had variable numbers of introns, ranging from 2 to 15. Cis-element analysis showed that the promoter of VvZFPs contained multiple cis-elements related to plant hormone response, stress resistance, and growth, among which the stress resistance elements were the predominant elements. Finally, the expression of VvZFP genes was determined using real-time quantitative PCR, which confirmed that the identified genes were involved in response to methyl jasmonate (MeJA), abscisic acid (ABA), salicylic acid (SA), and low-temperature (4 °C) stress. VvZFP10-GFP and VvZFP46-GFP fusion proteins were localized in the nucleus of tobacco cells, and VvZFP10 is the most responsive gene among all VvZFPs with the highest relative expression level to MeJA, ABA, SA and low-temperature (4 °C) stress. The present study provides a theoretical basis for exploring the mechanism of response to exogenous hormones and low-temperature tolerance in grapes and its molecular breeding in the future.

Entropy Confinement Promotes Hydrogenolysis Activity for Polyethylene Upcycling.

Chemical upcycling that catalyzes waste plastics back to high-purity chemicals holds great promise in end-of-life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state. This approach involves the synthesis of p-Ru/SBA catalysts, in which Ru nanoparticles are uniformly distributed within the channels of an SBA-15 support, using a precise impregnation method. The unique design of the p-Ru/SBA catalyst has demonstrated significant improvements in catalytic performance for the conversion of polyethylene into high-value liquid fuels, particularly diesel. The catalyst achieved a high solid conversion rate of 1106 g ⋅ gRu -1 ⋅ h-1 at 230 °C. Comparatively, this catalytic activity is 4.9 times higher than that of a control catalyst, Ru/SiO2 , and 14.0 times higher than that of a commercial catalyst, Ru/C, at 240 °C. This remarkable catalytic activity opens up immense opportunities for the chemical upcycling of waste plastics.

Ultra-Stable CsPbX3 @Pyrophosphate Nanoparticles in Water over One Year.

All-inorganic lead halide perovskite (CsPbX3 , X = Cl, Br, I, or their mixture) nanocrystals (NCs) have achieved inspiring advancements in optoelectronic fields but still suffer from poor durability when exposed to environmental stimuli such as water, irradiation and heat. Herein, a strategy of employing pyrophosphate as the inert shell for CsPbX3 NCs is reported. The strong binding between pyrophosphate and CsPbBr3 surface can stabilize the perovskite structure well. The as-obtained core@shell CsPbBr3 @NH4 AlP2 O7 NCs exhibit impressive stability against water and maintain the initial optical properties with negligible change in 400 days. Furthermore, significant improvement of irradiation/thermal resistance is realized due to the protecting role of pyrophosphate. The NCs can retain 100% and ≈90% of the original PL after hundreds of heating/cooling cycles and several hundred hours of UV light irradiation, respectively. As a result, the core@shell products can be directly used for high-resolution inkjet printing, enabling the printed fluorescent information to be resistant under harsh environmental conditions. This work provides a promising way for the synthesis of highly stable encapsulated perovskite NCs and demonstrates a great potential in practical applications.

One Stone Two Birds: Unlocking the Synergy between Amorphous Ni(OH)2 and Pd Nanocrystals toward Ethanol and Formic Acid Oxidation.

Even though extensive efforts have been devoted to mixing Pd nanocrystals with Ni(OH)2 for the enhanced synergy, it remains a great challenge to incorporate nanosized Ni(OH)2 species on the Pd electrode and reveal their synergy. Herein, we present spongelike Pd nanocrystals with the modification of amorphous Ni(OH)2 species. The catalyst configuration is first considered by compositing Pd with Ni(OH)2 species to optimize the Pd-Pd interatomic distance and then constructing a strongly coupled interface between Pd nanostructures and Ni(OH)2 species. For the ethanol oxidation reaction (EOR) and the formic acid oxidation reaction (FAOR), Pd-Ni(OH)2 composites exhibit an impressive mass activity of 4.98 and 2.65 A mgPd-1, respectively. Most impressively, there is no significant decrease in the EOR activity during five consecutive cycles (50 000 s). A series of CO-poisoning tests have proved that the enhanced EOR and FAOR performances involve synergy between Pd nanostructures and Ni(OH)2 species.

Suppressing Dehydroisomerization Boosts n-Butane Dehydrogenation with High Butadiene Selectivity.

Butadiene (BD) is a critical raw material in chemical industry, which is conventionally produced from naphtha cracking. The fast-growing demand of BD and the limited oil reserve motivate chemists to develop alternative methods for BD production. Shale gas, which mainly consists of light alkanes, has been considered as cheap raw materials to replace oil for BD production via n-butane direct dehydrogenation (n-BDH). However, the quest for highly-efficient catalysts for n-BDH is driven by the current drawback of low BD selectivity. Here, we demonstrate a strategy for boosting the selectivity of BD by suppressing dehydroisomerization, an inevitable step in the conventional n-BDH process which largely reduces the selectivity of BD. Detailed investigations show that the addition of alkali-earth metals (e. g., Mg and Ca) into Pt-Ga2 O3 /S10 catalysts increases Pt dispersity, suppresses coke deposition and dehydroisomerization, and thus leads to the significant increase of BD selectivity. The optimized catalyst displays an initial BD selectivity of 34.7 % at a n-butane conversion of 82.1 % at 625 °C, which outperforms the reported catalysts in literatures. This work not only provides efficient catalysts for BD production via n-BDH, but also promotes the researches on catalyst design in heterogeneous catalysis.

Cyclic nucleotide gated channel genes (CNGCs) in Rosaceae: genome-wide annotation, evolution and the roles on Valsa canker resistance.

KEY MESSAGE: In Rosaceae, tandem duplication caused the drastic expansion of CNGC gene family Group I. The members MdCN11 and MdCN19 negatively regulate Valsa canker resistance. Apple (Malus domestica) and pear (Pyrus bretschneideri and P. communis) are important fruit crops in Rosaceae family but are suffering from threats of Valsa canker. Cyclic nucleotide-gated ion channels (CNGCs) take crucial roles in plant immune responses. In the present study, a total of 355 CNGCs was identified from 8 Rosaceae plants. Based on phylogenetic analysis, 540 CNGCs from 18 plants (8 in Rosaceae and 10 others) could be divided into four groups. Group I was greatly expanded in Rosaceae resulted from tandem duplications. A large number of cis-acting regulatory elements (cis-elements) responsive to signals from multiple stresses and hormones were identified in the promoter regions of CNGCs in Malus spp. and Pyrus spp. Expressions of most Group I members were obviously up-regulated in Valsa canker susceptible varieties but not in the resistant ones. Furthermore, overexpression of the MdCN11 and MdCN19 in both apple fruits and 'Duli' (P. betulifolia) suspension cells compromised Valsa canker resistance. Overexpression of MdCN11 induced expression of hypersensitive response (HR)-related genes. In conclusion, tandem duplication resulted in a drastic expansion of CNGC Group I members in Rosaceae. Among these, MdCN11 and MdCN19 negatively regulate the Valsa canker resistance via inducting HR.

CircRNAs as promising biomarker in diagnosis of breast cancer: An updated meta-analysis.

BACKGROUND: Circular RNAs (circRNAs) have been identified to be involved in onset and progression of multiple malignant tumors. The present study aimed to systematically evaluate the diagnostic values of circRNAs in breast cancer. METHODS: The PubMed, Web of Science, Embase, CNKI, and Wanfang online databases were searched for the relevant studies before December 31, 2020. Statistical analysis of the diagnostic tests was performed based on STATA 16.0, Meta-DiSc 1.4, and RevMan 5.3 software. The threshold effect and publication bias were measured by the Spearman correlation and Deeks' funnel plot asymmetry test, respectively. RESULTS: Twenty-one studies from 13 articles were included in this meta-analysis. The pooled sensitivity and specificity were 0.77 and 0.71, respectively. The pooled positive likelihood ratio (PLR), negative likelihood ratio (NLR), and overall diagnostic odds ratio (DOR) were 2.6, 0.33, and 8, respectively. Furthermore, the area under the summary receiver operator characteristic curve was 0.80. In addition, down-regulated circRNAs achieved a diagnostic performance higher than up-regulated circRNAs, with area under curve (AUC) values of 0.81 and 0.74, respectively. Studies based on tissue samples presented better diagnostic accuracy than those based on plasma samples, with AUC values of 0.80 and 0.67. In addition, two circRNAs, including circ_0001073 and circTADA2A-E5/E6, showed higher diagnostic values, with AUC value of 0.990 and 0.937, respectively. According to the results of meta-regression, the case size (p<0.05) might be the source of the heterogeneity. CONCLUSION: CircRNAs exhibited a high diagnostic value for breast cancer and may function as potential diagnostic biomarkers for breast cancer.

Revealing the Correlation between Catalytic Selectivity and the Local Coordination Environment of Pt Single Atom.

Single atom catalysts (SACs) have recently attracted great attention in heterogeneous catalysis and have been regarded as ideal models for investigating the strong interaction between metal and support. Despite the huge progress over the past decade, the deep understanding on the structure-performance correlation of SACs at a single atom level still remains to be a great challenge. In this study, we demonstrate that the variation in the coordination number of the Pt single atom can significantly promote the propylene selectivity during propyne semihydrogenation (PSH) for the first time. Specifically, the propylene selectivity greatly increases from 65.4% to 94.1% as the coordination number of Pt-O increases from ∼3.4 to ∼5, whereas the variation in the coordination number of Pt-O slightly influences the turnover frequency values of SACs. We anticipate that the present work may deepen the understanding on the structure-performance of SACs and also promote the fundamental research in single atom catalysis.

Bismuth Oxyhydroxide-Pt Inverse Interface for Enhanced Methanol Electrooxidation Performance.

Developing efficient Pt-based electrocatalysts for the methanol oxidation reaction (MOR) is of pivotal importance for large-scale application of direct methanol fuel cells (DMFCs), but Pt suffers from severe deactivation brought by the carbonaceous intermediates such as CO. Here, we demonstrate the formation of a bismuth oxyhydroxide (BiOx(OH)y)-Pt inverse interface via electrochemical reconstruction for enhanced methanol oxidation. By combining density functional theory calculations, X-ray absorption spectroscopy, ambient pressure X-ray photoelectron spectroscopy, and electrochemical characterizations, we reveal that the BiOx(OH)y-Pt inverse interface can induce the electron deficiency of neighboring Pt; this would result in weakened CO adsorption and strengthened OH adsorption, thereby facilitating the removal of the poisonous intermediates and ensuring the high activity and good stability of Pt2Bi sample. This work provides a comprehensive understanding of the inverse interface structure and deep insight into the active sites for MOR, offering great opportunities for rational fabrication of efficient electrocatalysts for DMFCs.

Anthocyanin accumulation correlates with hormones in the fruit skin of 'Red Delicious' and its four generation bud sport mutants.

BACKGROUND: Bud sport mutants of apple (Malus domestica Borkh.) trees with a highly blushed colouring pattern are mainly caused by the accumulation of anthocyanins in the fruit skin. Hormones are important factors modulating anthocyanin accumulation. However, a good understanding of the interplay between hormones and anthocyanin synthesis in apples, especially in mutants at the molecular level, remains elusive. Here, physiological and comparative transcriptome approaches were used to reveal the molecular basis of color pigmentation in the skin of 'Red Delicious' (G0) and its mutants, including 'Starking Red' (G1), 'Starkrimson' (G2), 'Campbell Redchief' (G3) and 'Vallee spur' (G4). RESULTS: Pigmentation in the skin gradually proliferated from G0 to G4. The anthocyanin content was higher in the mutants than in 'Red Delicious'. The activation of early phenylpropanoid biosynthesis genes, including ASP3, PAL, 4CL, PER, CHS, CYP98A and F3'H, was more responsible for anthocyanin accumulation in mutants at the color break stage. In addition, IAA and ABA had a positive regulatory effect on the synthesis of anthocyanins, while GA had the reverse effect. The down-regulation of AACT1, HMGS, HMGR, MVK, MVD2, IDI1 and FPPS2 involved in terpenoid biosynthesis influences anthocyanin accumulation by positively regulating transcripts of AUX1 and SAUR that contribute to the synthesis of IAA, GID2 to GA, PP2C and SnRK2 to ABA. Furthermore, MYB and bHLH members, which are highly correlated (r=0.882-0.980) with anthocyanin content, modulated anthocyanin accumulation by regulating the transcription of structural genes, including CHS and F3'H, involved in the flavonoid biosynthesis pathway. CONCLUSIONS: The present comprehensive transcriptome analyses contribute to the understanding of the the relationship between hormones and anthocyanin synthesis as well as the molecular mechanism involved in apple skin pigmentation.

Advances in solar-driven, electro/photoelectrochemical, and microwave-assisted upcycling of waste polyesters.

Plastic waste in the environment causes significant environmental pollution. The potential of using chemical methods for upcycling plastic waste offers a dual solution to ensure resource sustainability and environmental restoration. This article provides a comprehensive overview of the latest technologies driven by solar-driven, electro/photoelectrochemical-catalytic, and microwave-assisted methods for the conversion of plastics into various valuable chemicals. It emphasizes selective conversion during the plastic transformation process, elucidates reaction pathways, and optimizes product selectivity. Finally, the article offers insights into the future developments of chemical upcycling of polyesters.

Hydrogen Bubbles: Harmonizing Local Hydrogen Transfer for Efficient Plastic Hydro-Depolymerization.

Hydro-depolymerization presents a promising avenue for transforming plastic waste into high-value hydrocarbons, offering significant potential for value-added recycling. However, a major challenge in this method arises from kinetic limitations due to insufficient hydrogen concentration near the active sites, requiring optimal catalytic performance only at higher hydrogen pressures. In this study, we address this hurdle by developing "hydrogen bubble catalysts" featuring Ru nanoparticles within mesoporous SBA-15 channels (Ru/SBA). The distinctive feature of Ru/SBA catalysts lies in their capacity for physical hydrogen storage and chemically reversible hydrogen spillover, ensuring a timely and ample hydrogen supply. Under identical reaction conditions, the catalytic activity of Ru/SBA surpassed that of Ru/SiO2 (no hydrogen storage capacity) by over 4-fold. This substantial enhancement in catalytic performance provides significant opportunities for near atmospheric pressure hydro-depolymerization of plastic waste.

Regulatory mechanism of GA3 application on grape (Vitis vinifera L.) berry size.

Gibberellin A3 (GA3) is often used as a principal growth regulator to increase plant size. Here, we applied Tween-20 (2%)-formulated GA3 (T1:40 mg/L; T2:70 mg/L) by dipping the clusters at the initial expansion phase of 'Red Globe' grape (Vitis vinifera L.) in 2018 and 2019. Tween-20 (2%) was used as a control. The results showed that GA3 significantly increased fruit cell length, cell size, diameter, and volume. The hormone levels of auxin (IAA) and zeatin (ZT) were significantly increased at 2 h (0 d) -1 d after application (DAA0-1) and remained significantly higher at DAA1 until maturity. Conversely, ABA exhibited an opposite trend. The mRNA and non-coding sequencing results yielded 436 differentially expressed mRNA (DE_mRNAs), 79 DE_lncRNAs and 17 DE_miRNAs. These genes are linked to hormone pathways like cysteine and methionine metabolism (ko00270), glutathione metabolism (ko00480) and plant hormone signal transduction (ko04075). GA3 application reduced expression of insensitive dwarf 2 (GID2, VIT_07s0129g01000), small auxin-upregulated RNA (SAUR, VIT_08s0007g03120) and 1-aminocyclopropane-1-carboxylate synthase (ACS, VIT_18s0001g08520), but increased SAUR (VIT_04s0023g00560) expression. These four genes were predicted to be negatively regulated by vvi-miR156, vvi-miR172, vvi-miR396, and vvi-miR159, corresponding to specific lncRNAs. Therefore, miRNAs could affect grape size by regulating key genes GID2, ACS and SAUR. The R2R3 MYB family member VvRAX2 (VIT_08s0007g05030) was upregulated in response to GA3 application. Overexpression of VvRAX2 in tomato transgenic lines increased fruit size in contrast to the wild type. This study provides a basis and genetic resources for elucidating the novel role of ncRNAs in fruit development.

Site-Selective Polyolefin Hydrogenolysis on Atomic Ru for Methanation Suppression and Liquid Fuel Production.

Catalytic hydrogenolysis of end-of-life polyolefins can produce value-added liquid fuels and therefore holds great promises in plastic waste reuse and environmental remediation. The major challenge limiting the recycling economic benefit is the severe methanation (usually >20%) induced by terminal C-C cleavage and fragmentation in polyolefin chains. Here, we overcome this challenge by demonstrating that Ru single-atom catalyst can effectively suppress methanation by inhibiting terminal C-C cleavage and preventing chain fragmentation that typically occurs on multi-Ru sites. The Ru single-atom catalyst supported on CeO2 shows an ultralow CH4 yield of 2.2% and a liquid fuel yield of over 94.5% with a production rate of 314.93 gfuels gRu -1 h-1 at 250 °C for 6 h. Such remarkable catalytic activity and selectivity of Ru single-atom catalyst in polyolefin hydrogenolysis offer immense opportunities for plastic upcycling.

Rationally designed nanoarray catalysts for boosted photothermal CO2 hydrogenation.

It is of emerging interest to convert CO2 and green H2 into solar fuels with great efficiency through photothermal CO2 hydrogenation. However, designing photothermal catalysts with improved sunlight harvesting ability, intrinsic catalytic activity, and thermal management to prevent heat dissipation still remains rather challenging. Herein, we report a facile structural engineering strategy for preparing efficient nanoarray-based photothermal catalysts with strong light absorption ability, high metal dispersity, and effective thermal management. Optimizing the 120 µm-SiNCs@Co catalyst allowed it to reach a record high Co-based photothermal CO2 conversion rate of 1780 mmol gCo-1 h-1. This study provides insight into the structural engineering of photothermal catalysts for enhanced catalytic performance and lays a foundation for efficient photothermal CO2 catalysis.

Unveiling the Local Structure and Electronic Properties of PdBi Surface Alloy for Selective Hydrogenation of Propyne.

Building a reliable relationship between the electronic structure of alloyed metallic catalysts and catalytic performance is important but remains challenging due to the interference from many entangled factors. Herein, a PdBi surface alloy structural model, by tuning the deposition rate of Bi atoms relative to the atomic interdiffusion rate at the interface, realizes a continuous modulation of the electronic structure of Pd. Using advanced X-ray characterization techniques, we provide a precise depiction of the electronic structure of the PdBi surface alloy. As a result, the PdBi catalysts show enhanced propene selectivity compared with the pure Pd catalyst in the selective hydrogenation of propyne. The prevented formation of saturated ß-hydrides in the subsurface layers and weakened propene adsorption on the surface contribute to the high selectivity. Our work provides in-depth understanding of the electronic properties of surface alloy structure and underlies the study of the electronic structure-performance relationship in bimetallic catalysts.

Mo2TiC2 MXene-Supported Ru Clusters for Efficient Photothermal Reverse Water-Gas Shift.

Driving metal-cluster-catalyzed high-temperature chemical reactions by sunlight holds promise for the development of negative-carbon-footprint industrial catalysis, which has yet often been hindered by the poor ability of metal clusters to harvest and utilize the full spectrum of solar energy. Here, we report the preparation of Mo2TiC2 MXene-supported Ru clusters (Ru/Mo2TiC2) with pronounced broadband sunlight absorption ability and high sintering resistance. Under illumination of focused sunlight, Ru/Mo2TiC2 can catalyze the reverse water-gas shift (RWGS) reaction to produce carbon monoxide from the greenhouse gas carbon dioxide and renewable hydrogen with enhanced activity, selectivity, and stability compared to their nanoparticle counterparts. Notably, the CO production rate of MXene-supported Ru clusters reached 4.0 mol·gRu-1·h-1, which is among the best reported so far for photothermal RWGS catalysts. Detailed studies suggest that the production of methane is kinetically inhibited by the rapid desorption of CO from the surface of the Ru clusters.