Constructing Metal(II)-Sulfate Site Catalysts toward Low Overpotential Carbon Dioxide Electroreduction to Fuel Chemicals.

Precise regulation of the active site structure is an important means to enhance the activity and selectivity of catalysts in CO2 electroreduction. Here, we creatively introduce anionic groups, which can not only stabilize metal sites with strong coordination ability but also have rich interactions with protons at active sites to modify the electronic structure and proton transfer process of catalysts. This strategy helps to convert CO2 into fuel chemicals at low overpotentials. As a typical example, a composite catalyst, CuO/Cu-NSO4/CN, with highly dispersed Cu(II)-SO4 sites has been reported, in which CO2 electroreduction to formate occurs at a low overpotential with a high Faradaic efficiency (-0.5 V vs. RHE, FEHCOO-=87.4%). Pure HCOOH is produced with an energy conversion efficiency of 44.3% at a cell voltage of 2.8 V. Theoretical modeling demonstrates that sulfate promotes CO2 transformation into a carboxyl intermediate followed by HCOOH generation, whose mechanism is significantly different from that of the traditional process via a formate intermediate for HCOOH production.

Highly Stable Pt/CeO2 Catalyst with Embedding Structure toward Water-Gas Shift Reaction.

Strong metal-support interaction (SMSI) has been extensively studied in heterogeneous catalysis because of its significance in stabilizing active metals and tuning catalytic performance, but the origin of SMSI is not fully revealed. Herein, by using Pt/CeO2 as a model catalyst, we report an embedding structure at the interface between Pt and (110) plane of CeO2, where Pt clusters (∼1.6 nm) are embedded into the lattice of ceria within 3-4 atomic layers. In contrast, this phenomenon is absent in the CeO2(100) support. This unique geometric structure, as an effective motivator, triggers more significant electron transfer from Pt clusters to CeO2(110) support accompanied by the formation of interfacial structure (Ptδ+-Ov-Ce3+), which plays a crucial role in stabilizing Pt nanoclusters. A comprehensive investigation based on experimental studies and theoretical calculations substantiates that the interfacial sites serve as the intrinsic active center toward water-gas shift reaction (WGSR), featuring a moderate strength CO activation adsorption and largely decreased energy barrier of H2O dissociation, accounting for the prominent catalytic activity of Pt/CeO2(110) (a reaction rate of 15.76 molCO gPt-1 h-1 and a turnover frequency value of 2.19 s-1 at 250 °C). In addition, the Pt/CeO2(110) catalyst shows a prominent durability within a 120 h time-on-stream test, far outperforming the Pt/CeO2(100) one, which demonstrates the advantages of this embedding structure for improving catalyst stability.

Carbonate Hydrogenated to Formate in the Aqueous Phase over Nickel/TiO2 Catalysts.

Carbonate hydrogenation to formate is a promising route to convert captured carbon dioxide into valuable chemicals, thus reducing carbon emissions and creating a revenue return. Developing inexpensive catalysts with high activity, selectivity, and stability remains challenging. We report a supported non-noble metal catalyst, Ni/TiO2 , with great selectivity over 96 % and excellent stability in catalyzing the conversion of carbonate into formate in aqueous solution. Ni0 and Ni2+ species are both observed in Ni/TiO2 catalysts, and the synergistic effect of these two Ni components leads to high activity and high selectivity of carbonate hydrogenation to formate.

Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation.

Single-site pincer-ligated iridium complexes exhibit the ability for C-H activation in homogeneous catalysis. However, instability and difficulty in catalyst recycling are inherent disadvantages of the homogeneous catalyst, limiting its development. Here, we report an atomically dispersed Ir catalyst as the bridge between homogeneous and heterogeneous catalysis, which displays an outstanding catalytic performance for n-butane dehydrogenation, with a remarkable n-butane reaction rate (8.8 mol·gIr-1·h-1) and high butene selectivity (95.6%) at low temperature (450 °C). Significantly, we correlate the BDH activity with the Ir species from nanoscale to sub-nanoscale, to reveal the nature of structure-dependence of catalyst. Moreover, we compare Ir single atoms with Pt single atoms and Pd single atoms for in-depth understanding the nature of metal-dependence at the atomic level. From experimental and theoretical calculations results, the isolated Ir site is suitable for both reactant adsorption/activation and product desorption. Its remarkable dehydrogenation capacity and moderate adsorption behavior are the key to the outstanding catalytic activity and selectivity.

Palladium single-atom catalysts synthesized by a gas-assisted redispersion strategy for efficient benzaldehyde hydrogenation.

A simple and efficient strategy was developed for the synthesis of Pd single-atom catalysts (PdSA/G) by nitric acid vapor-assisted redispersion. The as-prepared PdSA/G displayed robust catalytic performance in the selective hydrogenation reaction of benzaldehyde. This work paves a new way for the design of supported Pd single-atom catalysts.

Surface oxidation protection strategy of CoS2 by V2O5 for electrocatalytic hydrogen evolution reaction.

Transition metal sulfides (TMSs) are promising electrocatalysts for hydrogen evolution reaction (HER), while TMSs usually suffer from inevitable surface oxidation in air, and the impact of the surface oxidation on their HER catalytic activity remains unclear. Herein, we demonstrate an effective strategy for reducing the surface oxidation degree of easily oxidized CoS2 by introducing glued vanadium pentoxide (V2O5) nanoclusters, taking advantage of the preferential adsorption and strong interaction between high-valence V and O2. Combining oxidation protection and elaborate oxidation control experiments reveal that reduced surface oxidation degree of CoS2 is conducive to affording promising HER catalytic performance, as the oxidized surface of CoS2 can hinder the dissociation of water and thus is harmful to the HER process. Direct evidence is provided that surface oxidation should be carefully considered for TMS-based HER catalysts. The present work not only develops a new strategy for protecting CoS2 from surface oxidation, but also provides deep insight into the impact of surface oxidation on the HER performance of transition metal compounds.

Boosting CO hydrogenation towards C2+ hydrocarbons over interfacial TiO2-x/Ni catalysts.

Considerable attention has been drawn to tune the geometric and electronic structure of interfacial catalysts via modulating strong metal-support interactions (SMSI). Herein, we report the construction of a series of TiO2-x/Ni catalysts, where disordered TiO2-x overlayers immobilized onto the surface of Ni nanoparticles (~20 nm) are successfully engineered with SMSI effect. The optimal TiO2-x/Ni catalyst shows a CO conversion of ~19.8% in Fischer-Tropsch synthesis (FTS) process under atmospheric pressure at 220 °C. More importantly, ~64.6% of the product is C2+ paraffins, which is in sharp contrast to the result of the conventional Ni catalyst with the main product being methane. A combination study of advanced electron microscopy, multiple in-situ spectroscopic characterizations, and density functional theory calculations indicates the presence of Niδ-/TiO2-x interfacial sites, which could bind carbon atom strongly, inhibit methane formation and facilitate the C-C chain propagation, lead to the production of C2+ hydrocarbon on Ni surface.

Fully-exposed Pt-Fe cluster for efficient preferential oxidation of CO towards hydrogen purification.

Hydrogen is increasingly being discussed as clean energy for the goal of net-zero carbon emissions, applied in the proton-exchange-membrane fuel cells (PEMFC). The preferential oxidation of CO (PROX) in hydrogen is a promising solution for hydrogen purification to avoid catalysts from being poisoned by the trace amount of CO in hydrogen-rich fuel gas. Here, we report the fabrication of a novel bimetallic Pt-Fe catalyst with ultralow metal loading, in which fully-exposed Pt clusters bonded with neighbor atomically dispersed Fe atoms on the defective graphene surface. The fully-exposed PtFe cluster catalyst could achieve complete elimination of CO through PROX reaction and almost 100% CO selectivity, while maintaining good stability for a long period. It has the mass-specific activity of 6.19 (molCO)*(gPt)-1*h-1 at room temperature, which surpasses those reported in literatures. The exhaustive experimental results and theoretical calculations reveal that the construction of fully-exposed bimetallic Pt-Fe cluster catalysts with maximized atomic efficiency and abundant interfacial sites could facilitate oxygen activation on unsaturated Fe species and CO adsorption on electron-rich Pt clusters to hence the probability of CO oxidation, leading to excellent reactivity in practical applications.

Ptn-Ov synergistic sites on MoOx/γ-Mo2N heterostructure for low-temperature reverse water-gas shift reaction.

In heterogeneous catalysis, the interface between active metal and support plays a key role in catalyzing various reactions. Specially, the synergistic effect between active metals and oxygen vacancies on support can greatly promote catalytic efficiency. However, the construction of high-density metal-vacancy synergistic sites on catalyst surface is very challenging. In this work, isolated Pt atoms are first deposited onto a very thin-layer of MoO3 surface stabilized on γ-Mo2N. Subsequently, the Pt-MoOx/γ-Mo2N catalyst, containing abundant Pt cluster-oxygen vacancy (Ptn-Ov) sites, is in situ constructed. This catalyst exhibits an unmatched activity and excellent stability in the reverse water-gas shift (RWGS) reaction at low temperature (300 °C). Systematic in situ characterizations illustrate that the MoO3 structure on the γ-Mo2N surface can be easily reduced into MoOx (2 < x < 3), followed by the creation of sufficient oxygen vacancies. The Pt atoms are bonded with oxygen atoms of MoOx, and stable Pt clusters are formed. These high-density Ptn-Ov active sites greatly promote the catalytic activity. This strategy of constructing metal-vacancy synergistic sites provides valuable insights for developing efficient supported catalysts.

Low-Temperature Acetylene Semi-Hydrogenation over the Pd1-Cu1 Dual-Atom Catalyst.

The atomically dispersed metal catalyst or single-atom catalyst (SAC) with the utmost metal utilization efficiency shows excellent selectivity toward ethylene compared to the metal nanoparticles catalyst in the acetylene semi-hydrogenation reaction. However, these catalysts normally work at relatively high temperatures. Achieving low-temperature reactivity while preserving high selectivity remains a challenge. To improve the intrinsic reactivity of SACs, rationally tailoring the coordination environments of the first metal atom by coordinating it with a second neighboring metal atom affords an opportunity. Here, we report the fabrication of a dual-atom catalyst (DAC) that features a bonded Pd1-Cu1 atomic pair anchoring on nanodiamond graphene (ND@G). Compared to the single-atom Pd or Cu catalyst, it exhibits increased reactivity at a lower temperature, with 100% acetylene conversion and 92% ethylene selectivity at 110 °C. This work provides a strategy for designing DACs for low-temperature hydrogenation by manipulating the coordination environment of catalytic sites at the atomic level.

Building up libraries and production line for single atom catalysts with precursor-atomization strategy.

Having the excellent catalytic performance, single atom catalysts (SACs) arouse extensive research interest. However, the application of SACs is hindered by the lack of versatile and scalable preparation approaches. Here, we show a precursor-atomization strategy to produce SACs, involving the spray of droplets of solutions containing metal precursors onto support surface through ultrasonic atomization and the subsequent calcination. This approach is versatile to successful synthesis of a series of catalysts, including 19 SACs with different metal sites and supports and 3 derivatives of SACs (single atom alloys, double atom catalysts and bi-metallic SACs). Furthermore, it can be scaled up by a homemade production line with productivity over 1 kg day-1, and the well-controlled catalyst uniformity is evidenced by the identical characterization results and catalytic properties in Suzuki-Miyaura cross-coupling. This strategy lays a foundation for further investigation and may accelerate the trend from basic research to industrial applications of SACs.

Photocatalytic dehydrogenative C-C coupling of acetonitrile to succinonitrile.

The coupling of acetonitrile into succinonitrile, an important terminal dinitrile for value-added nylon production, via a dehydrogenative route is highly attractive, as it combines the valuable chemical synthesis with the production of green hydrogen energy. Here, we demonstrate that it is possible to achieve a highly selective light driven dehydrogenative coupling of acetonitrile molecules to synthesize succinonitrile using anatase TiO2 based photocatalysts in aqueous medium under mild conditions. Under optimized conditions, the formation rate of succinonitrile reaches 6.55 mmol/(gcat*h), with over 97.5% selectivity to target product. Mechanism studies reveal that water acts as cocatalyst in the reaction. The excited hole of anatase semiconductor oxidizes water forming hydroxyl radical, which subsequently assists the cleavage of sp3 C-H bond of acetonitrile to generate ·CH2CN radical for further C-C coupling. The synergy between TiO2 and Pt cocatalyst is important to enhance the succinonitrile selectivity and prevent undesirable over-oxidation and hydrolysis. This work offers an alternative route to prepare succinonitrile based on renewable energy under mild conditions and avoid the use of toxic reagents and stoichiometric oxidative radical initiators.

CO-tolerant RuNi/TiO2 catalyst for the storage and purification of crude hydrogen.

Hydrogen storage by means of catalytic hydrogenation of suitable organic substrates helps to elevate the volumetric density of hydrogen energy. In this regard, utilizing cheaper industrial crude hydrogen to fulfill the goal of hydrogen storage would show economic attraction. However, because CO impurities in crude hydrogen can easily deactivate metal active sites even in trace amounts such a process has not yet been realized. Here, we develop a robust RuNi/TiO2 catalyst that enables the efficient hydrogenation of toluene to methyl-cyclohexane under simulated crude hydrogen feeds with 1000-5000 ppm CO impurity at around 180 °C under atmospheric pressure. We show that the co-localization of Ru and Ni species during reduction facilitated the formation of tightly coupled metallic Ru-Ni clusters. During the catalytic hydrogenation process, due to the distinct bonding properties, Ru and Ni served as the active sites for CO methanation and toluene hydrogenation respectively. Our work provides fresh insight into the effective utilization and purification of crude hydrogen for the future hydrogen economy.

Fully-Exposed Pd Cluster Catalyst: An Excellent Catalytic Antibacterial Nanomaterial.

Exploring antibacterial nanomaterials with excellent catalytic antibacterial properties has always been a hot research topic. However, the construction of nanomaterials with robust antibacterial activity at the atomic level remains a great challenge. Here a fully-exposed Pd cluster atomically-dispersed on nanodiamond-graphene (Pdn /ND@G) with excellent catalytic antibacterial properties is reported. The fully-exposed Pd cluster nanozyme provides atomically-dispersed Pd cluster sites that facilitate the activation of oxygen. Notably, the oxidase-like catalytic performance of the fully-exposed Pd cluster nanozyme is much higher than that of Pd single-atom oxidase mimic, Pd nanoparticles oxidase mimic and even the previously reported palladium-based oxidase mimics. Under the density functional theory (DFT) calculations, the Pd cluster sites can efficiently catalyze the decomposition of oxygen to generate reactive oxygen species, resulting in strong antibacterial properties. This research provides a valuable insight to the design of novel oxidase mimic and antibacterial nanomaterial.

Catalytic Synthesis of Formamides by Integrating CO2 Capture and Morpholine Formylation on Supported Iridium Catalyst.

Herein we report an efficient and recyclable catalytic system for tandem CO2 capture and N-formylation to value-added chemicals. CO2 is apt to be captured by morpholine solution, while a highly efficient heterogeneous catalyst, isolated iridium atoms supported over nanadiamond/graphene, is discovered to be highly reactive for the formylation of morpholine, leading to the formation of N-formylmorpholine with excellent productivity (with a turnover number of 5 120 000 in a single batch reaction) and selectivity (>99 %). In addition, the CO2 captured by morpholine under atmospheric conditions can be converted to N-formylmorpholine with decent conversion (51 %), which realizes the integration of CO2 capture and conversion to value-added chemicals.

A Magnetically Separable Pd Single-Atom Catalyst for Efficient Selective Hydrogenation of Phenylacetylene.

Selective hydrogenation of alkynes to alkenes plays a crucial role in the synthesis of fine chemicals. However, how to achieve high selectivity and effective separation of the catalyst and substrate while obtaining high activity is the key for this reaction. In this work, a Pd single-atom catalyst is anchored to the shell of magnetic core-shell particles that consist of a Ni-nanoparticles core and a graphene sheets shell (Ni@G) for semi-hydrogenation of phenylacetylene, delivering 93% selectivity to styrene at full conversion with a robust turnover frequency of 7074 h-1 under mild reaction conditions (303 K, 2 bar H2 ). Moreover, the catalyst can be recovered promptly from the liquid phase due to its magnetic separability, which makes it present good stability for enduring five cycles. Experimental and theoretical investigations reveal that H2 and substrates are activated by atomically dispersed Pd atoms and Ni@G hybrid support, respectively. The hydrogenation reaction occurs on the surface of Ni@G via hydrogen spillover from the metal to the support. Such a strategy opens an avenue for designing highly active, selective, and magnetically recyclable catalysts for selective hydrogenation in liquid reaction systems.

Light-Induced Redox Looping of a Rhodium/Cex WO3 Photocatalyst for Highly Active and Robust Dry Reforming of Methane.

Dry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH4 and CO2 , into syngas. Here, we design a DRM photocatalyst Rh/Cex WO3 that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV-response photocatalysts, our photocatalyst produces a superior light-to-chemical energy efficiency (LTCEE) of 4.65 % with a moderate light intensity. We propose that a light-induced metal-to-metal charge transfer plays a crucial role in the DRM reaction, which induces a redox looping between Ce to W species to lower the activation energy. Quantum mechanical studies reveal that a high oxygen mobility of Cex WO3 , accompanied with the formation of oxo-bridge species, results in a substantial elimination of deposited C species during the reaction. Our catalyst design strategy could offer a promising energy-efficient industrial process for DRM.

Importance of Species Heterogeneity in Supported Metal Catalysts.

The structural heterogeneity of surface metal species, which is represented by the distribution in size, morphology, and local coordination environment of the active metal component, is almost inevitable in practical supported metal catalysts. This is often regarded as a major hindrance to the full utilization of metal loading and the high mass-specific catalytic activity. In this work, by quantitative evaluation of the individual reaction steps of a probe reaction, cyclohexanol dehydrogenation (an important reaction for hydrogen storage and transportation as well as high valued chemical production), we demonstrate that the inherent heterogeneity of supported Rhodium catalysts prepared by conventional synthesis has unique advantages in a complex heterogeneous catalytic reaction. The isolated Rh species (Rh1) is extremely active for the first step of dehydrogenation, the transformation of cyclohexanol to cyclohexanone, while the Rh ensemble sites (Rhe, including Rh clusters, Rhn, and Rh nanoparticles, Rhp) are highly efficient for the successive reaction step, cyclohexanone to phenol, for which the Rh1 sites are almost inactive. Only with the coexistence of both active structures could the optimal reaction performance be achieved, which ambiguously demonstrates the importance of species heterogeneity in some multistep catalytic reactions. Our study provides a new view of the benefits from structural heterogeneity in practical catalysts and sheds light on the catalyst design strategy for complex catalytic reactions.

Selective Catalytic Oxidation of Methane to Methanol in Aqueous Medium over Copper Cations Promoted by Atomically Dispersed Rhodium on TiO2.

Direct conversion of methane into value-added chemicals, such as methanol under mild conditions, is a promising route for industrial applications. In this work, atomically dispersed Rh on TiO2 suspended in an aqueous solution was used for the oxidation of methane to methanol. Promoted by copper cations (as co-catalyst) in solution, the catalysts exhibited high activity and selectivity for the production of methanol using molecular oxygen with the presence of carbon monoxide at 150 °C with a reaction pressure of 31 bar. Millimole level yields of methanol were reached with the selectivity higher than 99 % using the Rh/TiO2 catalysts with the promotion of the copper cation. CO was the reductive agent to generate H2 from H2 O, which led to the formation of H2 O2 through the reaction of H2 and O2 . Atomically dispersed Rh activated the C-H bond in CH4 and catalyzed the oxidation using H2 O2 . Copper cations maintained the low-valence state of Rh. Moreover, copper acted as a scavenger for suppressing the overoxidation, thus leading to the high selectivity of methanol.

Zeolite-Encaged Isolated Platinum Ions Enable Heterolytic Dihydrogen Activation and Selective Hydrogenations.

Understanding the unique behaviors of atomically dispersed catalysts and the origin thereof is a challenging topic. Herein, we demonstrate a facile strategy to encapsulate Ptδ+ species within Y zeolite and reveal the nature of selective hydrogenation over a Pt@Y model catalyst. The unique configuration of Pt@Y, namely atomically dispersed Ptδ+ stabilized by the surrounding oxygen atoms of six-membered rings shared by sodalite cages and supercages, enables the exclusive heterolytic activation of dihydrogen over Ptδ+···O2- units, resembling the well-known classical Lewis pairs. The charged hydrogen species, i.e., H+ and Hδ-, are active reagents for selective hydrogenations, and therefore, the Pt@Y catalyst exhibits remarkable performance in the selective hydrogenation of α,ß-unsaturated aldehydes to unsaturated alcohols and of nitroarenes to arylamines.