It is highly attractive but challenging to develop earth-abundant electrocatalysts for energy-saving electrolytic hydrogen generation. Herein, we report that Ni P nanoarrays grown in situ on nickel foam (Ni P/NF) behave as a durable high-performance non-noble-metal electrocatalyst for hydrazine oxidation reaction (HzOR) in alkaline media. The replacement of the sluggish anodic oxygen evolution reaction with such the more thermodynamically favorable HzOR enables energy-saving electrochemical hydrogen production with the use of Ni P/NF as a bifunctional catalyst for anodic HzOR and cathodic hydrogen evolution reaction. When operated at room temperature, this two-electrode electrolytic system drives 500 mA cm at a cell voltage as low as 1.0 V with strong long-term electrochemical durability and 100 % Faradaic efficiency for hydrogen evolution in 1.0 m KOH aqueous solution with 0.5 m hydrazine.

; for the Diabetic Retinopathy Clinical Research Network IMPORTANCE Ranibizumab is a viable treatment option for eyes with proliferative diabetic retinopathy (PDR) through 2 years. However, longer-term results are needed. OBJECTIVE To evaluate efficacy and safety of 0.5-mg intravitreous ranibizumab vs panretinal photocoagulation (PRP) over 5 years for PDR. DESIGN, SETTING, AND PARTICIPANTS Diabetic Retinopathy Clinical Research Network multicenter randomized clinical trial evaluated 394 study eyes with PDR enrolled February through December 2012. Analysis began in January 2018. INTERVENTIONS Eyes were randomly assigned to receive intravitreous ranibizumab (n = 191) or PRP (n = 203). Frequency of ranibizumab was based on a protocol-specified retreatment algorithm. Diabetic macular edema could be managed with ranibizumab in either group. MAIN OUTCOMES AND MEASURES Mean change in visual acuity (intention-to-treat analysis) was the main outcome. Secondary outcomes included peripheral visual field loss, development of vision-impairing diabetic macular edema, and ocular and systemic safety. RESULTS The 5-year visit was completed by 184 of 277 participants (66% excluding deaths). Of 305 enrolled participants, the mean (SD) age was 52 (12) years, 135 (44%) were women, and 160 (52%) were white. For the ranibizumab and PRP groups, the mean (SD) number of injections over 5 years was 19.2 (10.9) and 5.4 (7.9), respectively; the mean (SD) change in visual acuity letter score was 3.1 (14.3) and 3.0 (10.5) letters, respectively (adjusted difference, 0.6; 95% CI, −2.3 to 3.5; P = .68); the mean visual acuity was 20/25 (approximate Snellen equivalent) in both groups at 5 years. The mean (SD) change in cumulative visual field total point score was −330 (645) vs −527 (635) dB in the ranibizumab (n = 41) and PRP (n = 38) groups, respectively (adjusted difference, 208 dB; 95% CI, 9-408). Vision-impairing diabetic macular edema developed in 27 and 53 eyes in the ranibizumab and PRP groups, respectively (cumulative probabilities: 22% vs 38%; hazard ratio, 0.4; 95% CI, 0.3-0.7). No statistically significant differences between groups in major systemic adverse event rates were identified. CONCLUSIONS AND RELEVANCE Although loss to follow-up was relatively high, visual acuity in most study eyes that completed follow-up was very good at 5 years and was similar in both groups. Severe vision loss or serious PDR complications were uncommon with PRP or ranibizumab; however, the ranibizumab group had lower rates of developing vision-impairing diabetic macular edema and less visual field loss. Patient-specific factors, including anticipated visit compliance, cost, and frequency of visits, should be considered when choosing treatment for patients with PDR. These findings support either anti-vascular endothelial growth factor therapy or PRP as viable treatments for patients with PDR.

Heteratom doping is a possible way to tune the hydrogen evolution reaction (HER) catalytic capability of electrocatalysts. In this work, we report the development of Mn-doped CoP (Mn–Co–P) nanosheets array on Ti mesh (Mn–Co–P/Ti) as an efficient 3D HER electrocatalyst with good stability at all pH values. Electrochemical tests demonstrate that Mn doping leads to enhanced catalytic activity of CoP. In 0.5 M H2SO4, this Mn–Co–P/Ti catalyst drives 10 mA cm–2 at an overpotential of 49 mV, which is 32 mV less than that for CoP/Ti. To achieve the same current density, it demands overpotentials of 76 and 86 mV in 1.0 M KOH and phosphate-buffered saline, respectively. The enhanced HER activity for Mn–Co–P can be attributed to its more thermo-neutral hydrogen adsorption free energy than CoP, which is supported by density functional theory calculations.

As a non‐toxic species, Zn fulfills a multitude of biological roles, but its promoting effect on electrocatalysis has been rarely explored. Herein, the theoretic predications and experimental investigations that nonelectroactive Zn behaves as an effective promoter for CoP‐catalyzed hydrogen evolution reaction (HER) in both acidic and alkaline media is reported. Density function theory calculations reveal that Zn doing leads to more thermal‐neutral hydrogen adsorption free energy and thus enhanced HER activity for CoP catalyst. Electrochemical tests show that a Zn0.08Co0.92P nanowall array on titanium mesh (Zn0.08Co0.92P/TM) needs overpotentials of only 39 and 67 mV to drive a geometrical catalytic current of 10 mA cm‐2 in 0.5 m H2SO4 and 1.0 m KOH, respectively. This Zn0.08Co0.92P/TM is also superior in activity over CoP/TM for urea oxidation reaction (UOR), driving 115 mA cm‐2 at 0.6 V in 1.0 m KOH with 0.5 m urea. The high HER and UOR activity of this bifunctional electrode enables a Zn0.08Co0.92P/TM‐based two‐electrode electrolyzer for energy‐saving hydrogen production, offering 10 mA cm‐2 at a low voltage of 1.38 V with strong long‐term electrochemical stability.

The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm(-2) at an overpotential of 305 mV for hydrogen evolution and 100 mA cm(-2) at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm(-2) water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability.

The topotactic conversion of cobalt phosphide nanoarray on Ti mesh into a cobalt phosphate nanoarray (Co-Pi NA) via oxidative polarization in phosphate-buffered water is presented. As a 3D oxygen evolution reaction (OER) catalyst electrode at neutral pH, the resulting Co-Pi NA/Ti shows exceptionally high catalytic activity and demands an overpotential of only 450 mV to drive a geometrical catalytic current density of 10 mA cm . Notably, this catalyst also shows superior long-term electrochemical stability. The excellent catalytic activity can be attributed to that such 3D nanoarray configuration allows for the exposure of more active sites and the easier diffusion of electrolytes and oxygen.

Ni2P nanoflake arrays on carbon cloth act as an efficient and durable catalyst electrode for the urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Its two-electrode alkaline electrolyzer needs 1.35 V for 50 mA cm−2, which is 0.58 V less than that required for pure water splitting.

Heterostructures composed of two-dimensional black phosphorus (2D BP) with unique physical/chemical properties are of great interest. Herein, we report a simple solvothermal method to synthesize in-plane BP/Co P heterostructures for electrocatalysis. By using the reactive edge defects of the BP nanosheets as the initial sites, Co P nanocrystals are selectively grown on the BP edges to form the in-plane BP/Co P heterostructures. Owing to disposition on the original defects of BP, Co P improves the conductivity and offers more active electrocatalytic sites, so that the BP/Co P nanosheets exhibit better and more stable electrocatalytic activities in the hydrogen evolution and oxygen evolution reactions. Our work not only extends the application of BP to electrochemistry, but also provides a new idea to improve the performance of BP by utilization of defects. Furthermore, this strategy can be extended to produce other BP heterostructures to expand the corresponding applications.