Atomic Zn-Doping Induced Sabatier Optimum in NiZn0.03 Catalyst for CO2 Electroreduction at Industrial-Level Current Densities.

The Sabatier principle defines the essential criteria for an ideal catalyst in heterogeneous catalysis, while reaching the Sabatier optimum is still challenging in catalyst design. Herein, an elegant strategy is described to reach the Sabatier optimum of Ni electrocatalyst in CO2 reduction reaction (CO2 RR) by atomically Zn doping. The incorporation of 3% Zn single atom into Ni lattice leads to the moderate degrade of d-band center via Ni-Zn electronic coupling, which balances the bonding strengths of *COOH and *CO, resulting in a relative low energy barrier for CO2 activation while not being substantially poisoned by CO. Consequently, NiZn0.03 /C exhibits unique catalytic activity (jCO >100 mA cm-2 at -0.6 V), wide potential range for selective CO production (FECO >90% from -0.65 to -1.15 V), and outstanding long-term stability (FECO >90% during 85 h electrolysis at -0.85 V). The results provide valuable insights for the rational fabrication of superior non-noble bimetallic electrocatalysts in CO2 electroreduction.

Recent Advances in Regulating Ceramic Monolithic Catalyst Structure for Preferential Oxidation of CO in H2.

Preferential oxidation of CO (CO-PROX) has tremendous significance in purifying hydrogen for fuel cells to avoid catalyst poisoning by CO molecules. Traditional powder catalysts face numerous challenges, including high pressure drop, aggregation tendency, hotspot formation, poor mass and heat transfer efficiency, and inadequate thermal stability. Accordingly, ceramic monolithic catalysts, known as their excellent thermal stability, high surface area, and superior mass and heat transfer characteristics, are gaining increasing research attention. This review examines recent studies on ceramic monolithic catalysts in CO-PROX, placing emphasis on the regulation of active sites (e.g., precious metals like Pt and Au, and non-precious metals like CuO and CeO2), monolith structures, and coating strategies. In addition, the structure-catalytic performance relationships, as well as the potential and limitations of different ceramic monolithic catalysts in practical application, are discussed. Finally, the challenges of monolithic catalysts and future research prospects in CO-PROX reactions are highlighted.

Atomistic Insights into the Effect of Functional Groups on the Adsorption of Water by Activated Carbon for Heat Energy Storage.

Adsorption heat storage holds great promise for solar energy applications. The development of new adsorbent materials is currently the research focus in this area. The present work designs several activated carbon models with different functional groups, including -OH, -NH2, -COOH, and -SO3H, and explores the influence of functional groups' categories and numbers on the water adsorption capacity of the activated carbon using the GCMC method. The adsorption mechanism between functional groups and water molecules is analyzed using density functional theory. The results show that the functional groups could significantly improve the water adsorption capacity of activated carbon due to the hydrogen bond between functional groups and water molecules. In the scope of this paper, under low pressure, the activated carbon with -SO3H exhibits the best adsorption capacity, followed by the activated carbon with -COOH. Under low and medium pressure, increasing the number of -SO3H functional groups could increase the water adsorption capacity; however, when the pressure is high, increasing the functional group numbers might decrease the water adsorption capacity. As the temperature increases, the water adsorption capacity of activated carbons decreases, and the activated carbon with -SO3H is proven to have excellent application prospects in heat energy storage.

Tuning C1 /C2 Selectivity of CO2 Electrochemical Reduction over in-Situ Evolved CuO/SnO2 Heterostructure.

Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO2 electrochemical reduction (CO2 ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges to understanding the reaction mechanism and rationally designing catalysts. Herein, we for the first time elucidate the structural reconstruction of CuO/SnO2 under electrochemical potentials and reveal the intrinsic relationship between CO2 ER product selectivity and the in situ evolved heterostructures. At -0.85 VRHE , the CuO/SnO2 evolves to Cu2 O/SnO2 with high selectivity to HCOOH (Faradaic efficiency of 54.81 %). Mostly interestingly, it is reconstructed to Cu/SnO2-x at -1.05 VRHE with significantly improved Faradaic efficiency to ethanol of 39.8 %. In situ Raman spectra and density functional theory (DFT) calculations reveal that the synergetic absorption of *COOH and *CHOCO intermediates at the interface of Cu/SnO2-x favors the formation of *CO and decreases the energy barrier of C-C coupling, leading to high selectivity to ethanol.

Phosphorus Tailors the d-Band Center of Copper Atomic Sites for Efficient CO2 Photoreduction under Visible-Light Irradiation.

Photoreduction of CO2 into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single-Cu-atom catalysts with unique Cu configurations in phosphorus-doped carbon nitride (PCN), namely, Cu1 N3 @PCN and Cu1 P3 @PCN were fabricated via selective phosphidation, and tested in visible light-driven CO2 reduction by H2 O without sacrificial agents. Cu1 N3 @PCN was exclusively active for CO production with a rate of 49.8 µmolCO gcat -1 h-1 , outperforming most polymeric carbon nitride (C3 N4 ) based catalysts, while Cu1 P3 @PCN preferably yielded H2 . Experimental and theoretical analysis suggested that doping P in C3 N4 by replacing a corner C atom upshifted the d-band center of Cu in Cu1 N3 @PCN close to the Fermi level, which boosted the adsorption and activation of CO2 on Cu1 N3 , making Cu1 N3 @PCN efficiently convert CO2 to CO. In contrast, Cu1 P3 @PCN with a much lower Cu 3d electron energy exhibited negligible CO2 adsorption, thereby preferring H2 formation via photocatalytic H2 O splitting.

Bi-Functional Fe3 O4 /Au/CoFe-LDH Sandwich-Structured Electrocatalyst for Asymmetrical Electrolyzer with Low Operation Voltage.

The reduction of the overall electrolysis potential to produce hydrogen is a critical target for fabricating applicable hydrogen evolution cells. Sandwich-structured Fe3 O4 /Au/CoFe-LDH is synthesized via a spontaneous galvanic displacement reaction. A series of structural characterizations indicate the successful synthesis of sandwich-structured Fe3 O4 /Au/CoFe-LDH electrocatalyst. The trace amount of Au laying between Fe3 O4 and CoFe-LDH significantly improves the intrinsic conductivity and catalytic activity of the composite catalyst. In-depth investigations indicate that Fe3 O4 and CoFe-LDH are responsible for the electrocatalytic hydrogen evolution reaction (HER) whereas Au is responsible for the electrocatalytic glucose oxidation (GOR). The electrocatalytic tests indicate Fe3 O4 /Au/CoFe-LDH offers excellent electrocatalytic activity and stability for both HER and GOR, even at high current density (i.e., 1000 mA cm-2 ). Further electrochemistry examinations in a two-compartment cell with a two-electrode configuration show that Fe3 O4 /Au/CoFe-LDH can significantly reduce the overall potential for this asymmetrical cell, with only 0.48 and 0.89 V required to achieve 10 mA cm-2 current density with and without iR-compensation, which is the lowest overall potential requirement ever reported. The design and synthesis of Fe3 O4 /Au/CoFe-LDH pave a new way to electrochemically produce hydrogen and gluconate under extremely low cell voltage, which can readily match with a variety of solar cells.

Phosphorus Induced Electron Localization of Single Iron Sites for Boosted CO2 Electroreduction Reaction.

Electrochemical reduction of carbon dioxide (CO2 ) into chemicals and fuels has recently attracted much interest, but normally suffers from a high overpotential and low selectivity. In this work, single P atoms were introduced into a N-doped carbon supported single Fe atom catalyst (Fe-SAC/NPC) mainly in the form of P-C bonds for CO2 electroreduction to CO in an aqueous solution. This catalyst exhibited a CO Faradaic efficiency of ≈97 % at a low overpotential of 320 mV, and a Tafel slope of only 59 mV dec-1 , comparable to state-of-the-art gold catalysts. Experimental analysis combined with DFT calculations suggested that single P atom in high coordination shells (n≥3), in particular the third coordination shell of Fe center enhanced the electronic localization of Fe, which improved the stabilization of the key *COOH intermediate on Fe, leading to superior CO2 electrochemical reduction performance at low overpotentials.

Lacunary polyoxometalate oriented construction of dispersed Ni3S2 confined in WO3 for electrocatalytic water splitting.

Manufacturing low-cost, high-performance and earth-rich catalysts for hydrogen evolution (HER) and oxygen evolution reactions (OER) is critical to achieving sustainable green hydrogen production. Herein, we utilize lacunary Keggin-structure [PW9O34]9- (PW9) as a molecular pre-assembly platform to anchor Ni within a single PW9 molecule by vacancy-directed and nucleophile-induced effects for the uniform dispersion of Ni at the atomic level. The chemical coordination of Ni with PW9 can avoid the aggregation of Ni and favor the exposure of active sites. The Ni3S2 confined by WO3 prepared from controlled sulfidation of Ni6PW9/Nickel Foam (Ni6PW9/NF) exhibited excellent catalytic activity in both 0.5 M H2SO4 and 1 M KOH solutions, which required only 86 mV and 107 mV overpotentials for HER at a current density of 10 mA∙cm-2 and 370 mV for OER at 200 mA∙cm-2. This is attributed to the good dispersion of Ni at the atomic level induced by trivacant PW9 and the enhanced intrinsic activity by synergistic effect of Ni and W. Therefore, the construction of active phase from the atomic level is insightful to the rational design of dispersed and efficient electrolytic catalysts.

From atomic bonding to heterointerfaces: Co2P/WC constructed by lacunary polyoxometalates induced strategy as efficient hydrogen evolution electrocatalysts at all pH values.

Herein, a novel in-situ "atomic binding to heterointerface" strategy is proposed to obtain Co2P/WC@NC/CNTs catalyst with abundant heterointerface between cobalt phosphide and tungsten carbide (Co2P/WC) by the polyoxometalates (POMs)-based metal-organic frameworks (MOFs) precursor. The natural quasi interfaces in K10[Co4(H2O)2(PW9O34)2] molecule crucially guide the abundant Co2P/WC heterointerfaces down to atomic level. Meanwhile, MOFs cages can effectively encapsulate nanosized POMs at molecular level to control the size and dispersion of Co2P/WC nanoparticle, while carbon nanotubes (CNTs) enhance conductivity at nanoscale level. The interfacial electronic modulation between Co2P and WC lowering the energy barrier of the rate determining step, thus Co2P/WC@NC/CNTs showed reasonable hydrogen evolution reaction (HER) activity and stability in all-pH media including sea water. This work provides a "bottom-up" synthetic strategy for confined heterostructures, thus offering the prospect for more efficient interfacial charge modulation.

The facile synthesis of core-shell PtCu nanoparticles with superior electrocatalytic activity and stability in the hydrogen evolution reaction.

Pt is the most efficient electrocatalyst for the hydrogen evolution reaction (HER); however, it is a high cost material with scarce resources. In order to balance performance and cost in a Pt-based electrocatalyst, we prepared a series of PtCu bimetallic nanoparticles (NPs) with different Pt/Cu ratios through a facile synthetic strategy to optimize the utilization of Pt atoms. PtCu NPs demonstrate a uniform particle size distribution with exposed (111) facets that are highly active for the HER. A synergetic effect between Pt and Cu leads to electron transfer from Pt to Cu, which is favorable for the desorption of H intermediates. Therefore, the as-synthesized carbon black (CB) supported PtCu catalysts showed enhanced catalytic performance in the HER compared with a commercial Pt/C electrocatalyst. Typically, Pt1Cu3/CB showed excellent HER performance, with only 10 mV (acid) and 17 mV (alkaline) overpotentials required to achieve a current density of 10 mA cm-2. This is because the Pt1Cu3 NPs, with a small average particle size (7.70 ± 0.04 nm) and Pt-Cu core and Pt-rich shell structure, display the highest electrochemically active surface area (24.7 m2 gPt -1) out of the as-synthesized PtCu/CB samples. Furthermore, Pt1Cu3/CB showed good electrocatalytic stability, with current density drops of only 9.3% and 12.8% in acidic solution after 24 h and in alkaline solution after 9 h, respectively. This study may shed new light on the rational design of active and durable hydrogen evolution catalysts with low amounts of Pt.

Constructing RuCoOx /NC Nanosheets with Low Crystallinity within ZIF-9 as Bifunctional Catalysts for Highly Efficient Overall Water Splitting.

Electrocatalysts play a pivotal role in accelerating the sluggish electrochemical water splitting reaction. Herein, a Ru-Co oxides and carbon nitrides hybrid (RuCoOx /NC) electrocatalyst was constructed by employing ZIF-9 to disperse Ru precursor and deliberately regulating the calcination temperature. The moderate calcination temperature results in the RuCoOx nanocomposites with small particle size and low crystallinity as well as the co-existence of multi-valence metal compounds, thus boosting the amount and species of active sites. Moreover, the strong interactions between Co and Ru species induce the electron transfer from Co to Ru, thus enhancing the adsorption of anion intermediates on the electron-deficient Co species and the proton capturing capacity of electron-sufficient Ru species. As a result, the optimized RuCoOx /NC-350 catalyst behaved good electrocatalytic activities with 73 and 210 mV overpotential to achieve 10 mA cm-2 for HER and OER, respectively. Remarkably, it showed good durability by holding at 100 mA cm-2 for 100 h in HER and 50 mA cm-2 for 24 h in OER with small activity decline. This study may shed new light on the rational construction of highly efficient Ru-based catalysts for electrochemical water splitting.

Mesoporogen-Free Strategy to Construct Hierarchical TS-1 in a Highly Concentrated System for Gas-Phase Propene Epoxidation with H2 and O2.

Hierarchical TS-1 has attracted enormous attention from both academia and industry due to its remarkable catalytic performance in epoxidation reactions. However, sustainable synthesis of hierarchical-nanosized TS-1 without mesoporogens is still challenging. In this work, we report a facile and mesoporogen-free strategy to simultaneously manipulate pore structure and particle size of TS-1 employing the concentrated system. Taking advantage of the suspended nuclei in the concentrated system as confirmed by the DLS-PSD and atomic force microscopy, the novel TS-1 is demonstrated to have higher Ti concentration on surface, higher surface area (539 m2/g), abundant mesopores, and reduced crystal size (ca. 150 nm). Moreover, this Au-Ti bifunctional catalyst shows a good PO formation rate with enhanced catalytic stability due to the hierarchical structure. This strategy opens a novel way for the green synthesis of hierarchical-nanosized TS-1 and facilitates industrial development of the Au/TS-1 catalyst for propene epoxidation.

Regulating light olefins or aromatics production in ex-situ catalytic pyrolysis of biomass by engineering the structure of tin modified ZSM-5 catalyst.

Valorization of biomass to olefin or aromatics harbours tremendous practical value due to growing concerns about sustainable production of chemicals. Herein, the olefin or aromatics yields of ex-situ catalytic pyrolysis of pine can be regulated by impregnating Sn on hollow-structured ZSM-5 (M-ZSM-5) and microporous ZSM-5 catalysts in fixed-bed reactor, respectively. Results showed that Sn/ZSM-5 catalyst simultaneously increased medium acidic sites and maintained strong acidic sites, which obtained the maximum carbon yield of aromatics (33.77%) due to enhanced cracking and deoxygenation reactions. In addition, Sn boosted alkylation between olefin and aromatics, generating more alkylbenzene. In contrast, Sn/M-ZSM-5 catalyst produced the highest olefins carbon yield (12.39%) because the reduction of strong acidic sites and microporous volume inhibited the olefin aromatization. Moreover, olefins were easier to desorb from Sn/M-ZSM-5 due to the enhanced mass transfer ability, which weakened the alkylation reactions. The synergistic effect harbours great significance to manipulate the distribution of products.