Carbon-Boosted and Nitrogen-Stabilized Isolated Single-Atom Sites for Direct Dehydrogenation of Lower Alkanes.

Lower olefins are widely used in the chemical industry as basic carbon-based feedstocks. Here, we report the catalytic system featuring isolated single-atom sites of iridium (Ir1) that can function within the entire temperature range of 300-600 °C and transform alkanes with conversions close to thermodynamics-dictated levels. The high turnover frequency values of the Ir1 system are comparable to those of homogeneous catalytic reactions. Experimental data and theoretical calculations both indicate that Ir1 is the primary catalytic site, while the coordinating C and N atoms help to enhance the activity and stability, respectively; all three kinds of elements cooperatively contribute to the high performance of this novel active site. We have further immobilized this catalyst on particulate Al2O3, and we found that the resulting composite system under mimicked industrial conditions could still give high catalytic performances; in addition, we have also developed and established a new scheme of periodical in situ regeneration specifically for this composite particulate catalyst.

3D Oxide-Derived Ru Catalyst for Ultra-Efficient Hydrogenation of Levulinic Acid to γ-Valerolactone.

γ-valerolactone (GVL) is a key value-added chemical catalytically produced from levulinic acid (LA), an important biomass derivative platform chemical. Here an ultra-efficient 3D Ru catalyst generated by in situ reduction of RuZnOx nanoboxes is reported; the catalyst features a well-defined structure of highly dispersed in situ oxide-derived Ru (IOD-Ru) clusters (≈1 nm in size) spatially confined within the 3D nanocages with rich mesopores, which guarantees a maximized atom utilization with a high exposure of Ru active sites as well as a 3D accessibility for substrate molecules. The IOD-Ru exhibits ultrahigh performance for the hydrogenation of LA into GVL with a record-breaking turnover frequency (TOF) up to 59400 h-1 , 14 times higher than that of the ex situ reduction of RuZnOx nanoboxes catalyst. Structural characterizations and theoretical calculations collectively indicate that the defect-rich and coordination-unsaturated IOD-Ru sites can boost the activation of the carbonyl group in LA with a significantly lowered energy barrier of hydrogenation.

Direct Microenvironment Modulation of CO2 Electroreduction: Negatively Charged Ag Sites Going beyond Catalytic Surface Reactions.

Electrochemical reduction of CO2 is an important way to achieve carbon neutrality, and much effort has been devoted to the design of active sites. Apart from elevating intrinsic activity, expanding the functionality of active site may also boost catalytic performance. Here we have designed "negatively charged Ag (nc-Ag)" active sites featuring both the intrinsic activity and the capability of regulating microenvironment, through modifying Ag nanoparticles with atomically dispersed Sn species. Different from conventional active sites (which only govern surface process by bonding with the intermediates), the nc-Ag sites could manipulate environmental species. Therefore, the sites could not only activate CO2, but also regulate interfacial H2O and CO2, as confirmed by operando spectroscopies. The catalyst delivers a high current density with CO faradaic efficiency of 97%. Our work here opens up new opportunities for the design of multifunctional electrocatalytic active sites.

Stabilizing Copper by a Reconstruction-Resistant Atomic Cu-O-Si Interface for Electrochemical CO2 Reduction.

Copper (Cu), a promising catalyst for electrochemical CO2 reduction (CO2R) to multi-electron reduction products, suffers from an unavoidable and uncontrollable reconstruction process during the reaction, which not only may lead to catalyst deactivation but also brings great challenges to the exploration of the structure-performance relationship. Herein, we present an efficient strategy for stabilizing Cu with silica and synthesize reconstruction-resistant CuSiOx amorphous nanotube catalysts with abundant atomic Cu-O-Si interfacial sites. The strong interfacial interaction between Cu and silica makes the Cu-O-Si interfacial sites ultrastable in the CO2R reaction without any apparent reconstruction, thus exhibiting high CO2-to-CH4 selectivity (72.5%) and stability (FECH4 remains above 60% after 12 h of test). A remarkable CO2-to-CH4 conversion rate of 0.22 µmol cm-2 s-1 was also achieved in a flow cell device. This work provides a very promising route for the design of highly active and stable Cu-based CO2R catalysts.

Heterogeneous Iridium Single-Atom Molecular-like Catalysis for Epoxidation of Ethylene.

Developing efficient and simple catalysts to reveal the key scientific issues in the epoxidation of ethylene has been a long-standing goal for chemists, whereas a heterogenized molecular-like catalyst is desirable which combines the best aspects of homogeneous and heterogeneous catalysts. Single-atom catalysts can effectively mimic molecular catalysts on account of their well-defined atomic structures and coordination environments. Herein, we report a strategy for selective epoxidation of ethylene, which exploits a heterogeneous catalyst comprising iridium single atoms to interact with the reactant molecules that act analogously to ligands, resulting in molecular-like catalysis. This catalytic protocol features a near-unity selectivity (99%) to produce value-added ethylene oxide. We investigated the origin of the improvement of selectivity for ethylene oxide for this iridium single-atom catalyst and attributed the improvement to the π-coordination between the iridium metal center with a higher oxidation state and ethylene or molecular oxygen. The molecular oxygen adsorbed on the iridium single-atom site not only helps to strengthen the adsorption of ethylene molecule by iridium but also alters its electronic structure, allowing iridium to donate electrons into the double bond π* orbitals of ethylene. This catalytic strategy facilitates the formation of five-membered oxametallacycle intermediates, leading to the exceptionally high selectivity for ethylene oxide. Our model of single-atom catalysts featuring remarkable molecular-like catalysis can be utilized as an effective strategy for inhibiting the overoxidation of the desired product. Implementing the concepts of homogeneous catalysis into heterogeneous catalysis would provide new perspectives for the design of new advanced catalysts.

Engineering Molecular Heterostructured Catalyst for Oxygen Reduction Reaction.

Introducing a second metal species into atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts to construct diatomic sites (DASs) is an effective strategy to elevate their activities and stabilities. However, the common pyrolysis-based method usually leads to substantial uncertainty for the formation of DASs, and the precise identification of the resulting DASs is also rather difficult. In this regard, we developed a two-step specific-adsorption strategy (pyrolysis-free) and constructed a DAS catalyst featuring FeCo "molecular heterostructures" (FeCo-MHs). In order to rule out the possibility of the two apparently neighboring (in the electron microscopy image) Fe/Co atoms being dispersed respectively on the top/bottom surfaces of the carbon support and thus forming "false" MHs, we conducted in situ rotation (by 8°, far above the critical angle of 5.3°) and directly identified the individual FeCo-MHs. The formation of FeCo-MHs could modulate the magnetic moments of the metal centers and increase the ratio of low-spin Fe(II)-N4 moiety; thus the intrinsic activity could be optimized at the apex of the volcano-plot (a relationship as a function of magnetic moments of metal-phthalocyanine complexes and catalytic activities). The FeCo-MHs catalyst displays an exceptional ORR activity (E1/2 = 0.95 V) and could be used to construct high-performance cathodes for hydroxide exchange membrane fuel cells and zinc-air batteries.

Crystal structure of the 3-ketodihydrosphingosine reductase TSC10 from Cryptococcus neoformans.

The second step in the de novo sphingolipid biosynthesis is the reduction of 3-ketodihydrosphingosine by 3-ketodihydrosphingosine reductase (KDSR) to produce dihydrosphingosine (sphinganine). Fungal TSC10 and mammalian KDSR (also named FVT-1) proteins are the enzymes responsible for this process and they belong to the short-chain dehydrogenase/reductase (SDR) superfamily. Albeit that both fungal and mammalian 3-ketodihydrosphingosine reductases were identified more than a decade ago, no structure of these enzymes from any species has been experimentally determined. Here we report the crystal structure of the catalytic domain of TSC10 from Cryptococcus neoformans in complex with NADPH. cnTSC10 adopts a Rossmann fold with a central seven-stranded ß-sheet flanked by α-helices on both sides. Several regions are disordered that include the segment connecting the serine and tyrosine residues of the catalytic triad, the so-called 'substrate loop', and the C-terminal region that often participates in homo-tetramerization in other SDRs. In addition, the cofactor NADPH is not fully ordered. These structural features indicate that the catalytic site of cnTSC10 possesses significant flexibility. cnTSC10 is predominantly dimeric in solution while a minor portion of the protein forms homo-tetramer. The crystal structure reveals that the homo-dimer interface involves both hydrophobic and hydrophilic interactions mediated by helices α4 and α5, as well as the loop connecting strand ß4 and helix α4. Because residues forming hydrogen bonds and salt bridges in the dimer interface are not conserved between fungal TSC10 and mammalian KDSR proteins, it might be possible to develop inhibitors that selectively target fungal TSC10 dimerization.

Engineering Lattice Disorder on a Photocatalyst: Photochromic BiOBr Nanosheets Enhance Activation of Aromatic C-H Bonds via Water Oxidation.

Solar-driven photocatalytic reactions can mildly activate hydrocarbon C-H bonds to produce value-added chemicals. However, the inefficient utilization of photogenerated carriers hinders the application. Here, we report reversible photochromic BiOBr (denoted as p-BiOBr) nanosheets that were colored by trapping photogenerated holes upon visible light irradiation and bleached by water oxidation to generate hydroxyl radicals, demonstrating enhanced carrier separation and water oxidation. The photocatalytic coupling and oxidation reactions of ethylbenzene were efficiently realized by p-BiOBr in a water-based medium under ambient temperature and pressure (apparent quantum yield is 14 times that of pristine BiOBr). The p-BiOBr nanosheets feature lattice disordered defects on the surface, providing rich uncoordinated catalytic sites and inducing structural distortions and lattice strain, which further leads to an altered band structure and significantly enhanced photocatalytic performances. These hole-trapping materials open up the possibility of substantially elevating the utilization efficiency of photogenerated holes for high-efficiency photocatalytic activation of various saturated C-H bonds.

Cobalt Single Atom Incorporated in Ruthenium Oxide Sphere: A Robust Bifunctional Electrocatalyst for HER and OER.

The development of highly active and stable bifunctional noble-metal-based electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is a crucial goal for clean and renewable energy, which still remains challenging. Herein, we report an efficient and stable catalyst comprising a Co single atom incorporated in an RuO2 sphere for HER and OER, in which the Co single atom in the RuO2 sphere was confirmed by XAS, AC-STEM, and DFT. This tailoring strategy uses a Co single atom to modify the electronic structures of the surrounding Ru atoms and thereby remarkably elevates the electrocatalytic activities. The catalyst requires ultralow overpotentials, 45 mV for HER and 200 mV for OER, to deliver a current density of 10 mA cm-2 . The theoretical calculations reveal that the energy barriers for HER and OER are lowered after incorporation of a cobalt single atom.

Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation.

Electrocatalysis plays a central role in clean energy conversion, enabling a number of processes for future sustainable technologies. Atomic site electrocatalysts (ASCs), including single-atomic site catalysts (SASCs) and diatomic site catalysis (DASCs), are being pursued as economical alternatives to noble-metal-based catalysts for these reactions by virtue of their exceptionally high atom utilization efficiencies, well-defined active sites and high selectivities. In this review, we start from a systematic review on the fabrication routes of ASCs followed by an overview of some new and effective characterization methods to precisely probe the atomic structure. Then we give a comprehensive summary on the current advances in some typical clean energy reactions: water splitting, including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER); oxygen reduction reaction (ORR), including selective 4e- - ORR toward H2O/OH- and 2e- - ORR toward H2O2/HO2-; selective electrooxidation of formic acid, methanol and ethanol (FAOR, MOR and EOR). At the end of this paper, we present a brief conclusion, and discuss the challenges and opportunities on the further development of more selective, active, stable and less expensive ASCs.

Synergistically Interactive Pyridinic-N-MoP Sites: Identified Active Centers for Enhanced Hydrogen Evolution in Alkaline Solution.

For electrocatalysts for the hydrogen evolution reaction (HER), encapsulating transition metal phosphides (TMPs) into nitrogen-doped carbon materials has been known as an effective strategy to elevate the activity and stability. Yet still, it remains unclear how the TMPs work synergistically with the N-doped support, and which N configuration (pyridinic N, pyrrolic N, or graphitic N) contributes predominantly to the synergy. Here we present a HER electrocatalyst (denoted as MoP@NCHSs) comprising MoP nanoparticles encapsulated in N-doped carbon hollow spheres, which displays excellent activity and stability for HER in alkaline media. Results of experimental investigations and theoretical calculations indicate that the synergy between MoP and the pyridinic N can most effectively promote the HER in alkaline media.

Intrinsic Broadband White-Light Emission from Ultrastable, Cationic Lead Halide Layered Materials.

We report a family of cationic lead halide layered materials, formulated as [Pb2 X2 ]2+ [- O2 C(CH)2 CO2- ] (X=F, Cl, Br), exhibiting pronounced broadband white-light emission in bulk form. These well-defined PbX-based structures achieve an external quantum efficiency as high as 11.8 %, which is comparable to the highest reported value (ca.9 %) for broadband phosphors based on layered organolead halide perovskites. More importantly, our cationic materials are ultrastable lead halide materials, which overcome the air/moisture-sensitivity problems of lead perovskites. In contrast to the perovskites and other bulk emitters, the white-light emission intensity of our materials remains undiminished after continuous UV irradiation for 30 days under atmospheric conditions (ca.60 % relative humidity). Our mechanistic studies confirm that the broadband emission is ascribed to short-range electron-phonon coupling in the strongly deformable lattice and generated self-trapped carriers.

Customizing catalyst surface/interface structures for electrochemical CO2 reduction.

Electrochemical CO2 reduction reaction (CO2RR) provides a promising route to converting CO2 into value-added chemicals and to neutralizing the greenhouse gas emission. For the industrial application of CO2RR, high-performance electrocatalysts featuring high activities and selectivities are essential. It has been demonstrated that customizing the catalyst surface/interface structures allows for high-precision control over the microenvironment for catalysis as well as the adsorption/desorption behaviors of key reaction intermediates in CO2RR, thereby elevating the activity, selectivity and stability of the electrocatalysts. In this paper, we review the progress in customizing the surface/interface structures for CO2RR electrocatalysts (including atomic-site catalysts, metal catalysts, and metal/oxide catalysts). From the perspectives of coordination engineering, atomic interface design, surface modification, and hetero-interface construction, we delineate the resulting specific alterations in surface/interface structures, and their effect on the CO2RR process. At the end of this review, we present a brief discussion and outlook on the current challenges and future directions for achieving high-efficiency CO2RR via surface/interface engineering.

Rational design of atomic site catalysts for electrochemical CO2 reduction.

Renewable-energy-powered electrochemical CO2 reduction (ECR) is a promising way of transforming CO2 to value-added products and achieving sustainable carbon recycling. By virtue of the extremely high exposure rate of active sites and excellent catalytic performance, atomic site catalysts (ASCs), including single-atomic site catalysts and diatomic site catalysts, have attracted considerable attention. In this feature article, we focus on the rational design strategies of ASCs developed in recent years for the ECR reaction. The influence of these strategies on the activity and selectivity of ASCs for ECR is further discussed in terms of electronic regulation, synergistic activation, microenvironmental regulation and tandem catalytic system construction. Finally, the challenges and future directions are indicated. We hope that this feature article will be helpful in the development of novel ASCs for ECR.

Metal-organic framework derived FeNi alloy nanoparticles embedded in N-doped porous carbon as high-performance bifunctional air-cathode catalysts for rechargeable zinc-air battery.

Developing efficient and durable bifunctional air-cathode catalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key efforts promoting the practical rechargeable zinc-air batteries (ZABs). In this paper, high-performance bifunctional air-cathode catalysts by a two-step strategy: atomically dispersed Ni on N-doped carbon is first derived from MOF to form uniformly dispersed NiNC, which are pyrolyzed together with Fe source at different high-temperatures to form FeNi@NC-T (T = 800, 900, and 1000 °C) catalysts. The as-synthesized non-noble metal FeNi@NC-900 catalyst exhibits a considerably small potential gap (ΔE) of 0.72 V between ORR and OER, which is as the same as commercial noble metal Pt/C + Ir black mixed catalyst. The performance of the ZABs using FeNi@NC-900 as the air-cathode catalyst displays a power density of 119 mW·cm-2 and a specific capacity of 830.1 mAh·g-1, which is superior to that of Pt/C + Ir black mixed catalyst. This work provides a guideline for designing alloy electrocatalysts with uniform size and nanoparticle distribution for metal-air batteries with bifunctional air-cathodes.

Nature-Inspired Design of Molybdenum-Selenium Dual-Single-Atom Electrocatalysts for CO2 Reduction.

Electrochemical CO2 reduction (ECR) is becoming an increasingly important technology for achieving carbon neutrality. Inspired by the structure of naturally occurring Mo-dependent enzymes capable of activating CO2 , a heteronuclear Mo-Se dual-single-atom electrocatalyst (MoSA-SeSA) for ECR into CO with a Faradaic efficiency of above 90% over a broad potential window from -0.4 to -1.0 V versus reversible hydrogen electrode is demonstrated here. Both operando characterization and theoretical simulation results verify that MoSA acts as central atoms that directly interact with the ECR feedstock and intermediates, whereas the SeSA adjacent to MoSA modulates the electronic structure of MoSA through long-range electron delocalization for inhibiting MoSA poisoning caused by strong CO adsorption. In addition, the SeSAs far from MoSA help suppress the competing hydrogen evolution side reaction and accelerate the CO2 transport by repelling H2 O. This work provides new insight into the precise regulation and in-depth understanding of multisite synergistic catalysis at the atomic scale.

Distinct Crystal-Facet-Dependent Behaviors for Single-Atom Palladium-On-Ceria Catalysts: Enhanced Stabilization and Catalytic Properties.

High-performance, fully atomically dispersed single-atom catalysts (SACs) are promising candidates for next-generation industrial catalysts. However, it remains a great challenge to avoid the aggregation of isolated atoms into nanoparticles during the preparation and application of SACs. Here, the evolution of Pd species is investigated on different crystal facets of CeO2 , and vastly different behaviors on the single-atomic dispersion of surface Pd atoms are surprisingly discovered. In situ X-ray photoelectron spectroscopy (XPS), in situ near-ambient-pressure-XPS (NAP-XPS), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray absorption spectroscopy (XAS) reveal that, in a reducing atmosphere, more oxygen vacancies are generated on the (100) facet of CeO2 , and Pd atoms can be trapped and thus feature atomic dispersion; by contrast, on the CeO2 (111) facet, Pd atoms will readily aggregate into clusters (Pdn ). Furthermore, Pd1 /CeO2 (100) gives a high selectivity of 90.3% for the catalytic N-alkylation reaction, which is 2.8 times higher than that for Pdn /CeO2 (111). This direct evidence demonstrates the crucial role of crystal-facet effects in the preparation of metal-atom-on-metal-oxide SACs. This work thus opens an avenue for the rational design and targeted synthesis of ultrastable and sinter-resistant SACs.

Interfacial water engineering boosts neutral water reduction.

Hydrogen evolution reaction (HER) in neutral media is of great practical importance for sustainable hydrogen production, but generally suffers from low activities, the cause of which has been a puzzle yet to be solved. Herein, by investigating the synergy between Ru single atoms (RuNC) and RuSex cluster compounds (RuSex) for HER using ab initio molecular dynamics, operando X-ray absorption spectroscopy, and operando surface-enhanced infrared absorption spectroscopy, we establish that the interfacial water governs neutral HER. The rigid interfacial water layer in neutral media would inhibit the transport of H2O*/OH* at the electrode/electrolyte interface of RuNC, but the RuSex can promote H2O*/OH* transport to increase the number of available H2O* on RuNC by disordering the interfacial water network. With the synergy of RuSex and RuNC, the resulting neutral HER performance in terms of mass-specific activity is 6.7 times higher than that of 20 wt.% Pt/C at overpotential of 100 mV.

Anion-exchange-mediated internal electric field for boosting photogenerated carrier separation and utilization.

Heterojunctions modulated internal electric field (IEF) usually result in suboptimal efficiencies in carrier separation and utilization because of the narrow IEF distribution and long migration paths of photocarriers. In this work, we report distinctive bismuth oxyhydroxide compound nanorods (denoted as BOH NRs) featuring surface-exposed open channels and a simple chemical composition; by simply modifying the bulk anion layers to overcome the limitations of heterojunctions, the bulk IEF could be readily modulated. Benefiting from the unique crystal structure and the localization of valence electrons, the bulk IEF intensity increases with the atomic number of introduced halide anions. Therefore, A low exchange ratio (~10%) with halide anions (I-, Br-, Cl-) gives rise to a prominent elevation in carrier separation efficiency and better photocatalytic performance for benzylamine coupling oxidation. Here, our work offers new insights into the design and optimization of semiconductor photocatalysts.

Manganese vacancy-confined single-atom Ag in cryptomelane nanorods for efficient Wacker oxidation of styrene derivatives.

Single-atom catalysts provide a pathway to elucidate the nature of catalytically active sites. However, keeping them stabilized during operation proves to be challenging. Herein, we employ cryptomelane-type octahedral molecular sieve nanorods featuring abundant manganese vacancy defects as a support, to periodically anchor single-atom Ag. The doped Ag atoms with tetrahedral coordination are found to locate at cation substitution sites rather than being supported on the catalyst surface, thus effectively tuning the electronic structure of adjacent manganese atoms. The resulting unique Ag-O-MnO x unit functions as the active site. Its turnover frequency reaches 1038 h-1, one order of magnitude higher than for previously reported catalysts, with 90% selectivity for anti-Markovnikov phenylacetaldehyde. Mechanistic studies reveal that the activation of styrene on the ensemble site of Ag-O-MnO x is significantly promoted, which can accelerate the oxidation of styrene and, in particular, the rate-determining step of forming the epoxide intermediate. Such an extraordinary electronic promotion can be extended to other single-atom catalysts and paves the way for their practical applications.